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ESSENTIALS OF CHEMISTEY.

BY

JOHN

C.

HESSLER, PH.D.

PROFESSOR OF CHEMISTRY,* JAMES MILLIKIN UNIVERSITY LATE INSTRUCTOR IN CHEMISTRY, THE UNIVERSITY OF CHICAGO, AND THE HYDE PARK (CHICAGO) HIGH SCHOOL

WE

ALBERT

L.

SMITH, PH.D.

INSTRUCTOR IN CHEMISTRY, THE ENGLEWCOD HIGH SCHOOL, CHICAGO

BEVISED EDITION
BY

(1912)

JOHN

C.

HESSLER

ov /roXX*

a\\A

BENJ. H.
BOSTON

SANBORN &
NEW YORK
1912

CO.
CHICAGO

Copyright, 1912.

BY JOHN

C.

HESSLER.

yrraa SAMUEL USHER 176 TO 184 HIGH STREET


BOSTON, MASS.

Sltr jForl ifiil

PREFACE.
The Revised Edition
"
of the

"

Essentials of Chemis-

retains the scientific character of the original try text, but the method of treatment and the order of topics have been modified in accordance with the

These years have about significant changes in the Chemistry brought Not only has the of courses secondary schools. number of students increased greatly, but chemical science has become more and more important as
experience of the past ten years.

a prerequisite for work in the other sciences and in applied courses. In view of this increased and altered

demand for chemical instruction, authors are tempted


to neglect the basic principles of the science,

and

to

But enlarge upon the purely descriptive matter. that is is not an ademerely descriptive Chemistry
is

quate preparation even for applied courses. What sought of Chemistry, both by those who study it as a prerequisite for other work, and by those whose
sole

aim

is

general culture,

cal point of view.

To

essentially, the chemipresent that point of view


is,

properly, a text-book must include a correct, even if simple, treatment of chemical theory. Especially

251954

IV

PREFACE.

it include recent physico-chemical conceptions, such as equilibrium, that have a general application to both physical and chemical changes. The revision of the " Essentials " has been made with the purpose of meeting these demands. The

must

most important changes and additions are the following:


1.

theoretical matter has been presented than in the original edition, and it has been broken up into portions more suitable for study and assimilation. Chapter I contains, besides the specifiearlier

The

cally chemical topics of changes, elements, etc., a short account of matter, energy, mass, and density.

The

idea that energy


is

substances

Oxygen. Problems on the relation of volume to temperature

is associated with matter in in Chapter II, that on out brought The gas laws are given in Chapter III.

and pressure are solved by the fractional method rather than by the method of proportions. The laws of definite proportions and of equivalent weights are given in the chapter on Water (V). The law of multiple proportions and the atomic and molecular
Chapter VIII and of calculations from formulas and equations. The methods for determining molecular weights are given in Chapter XII; those for atomic weights, in Chapter XIII. Molecular
hypotheses appear in Chapter VII.
treats of equations

formulas

and equations,

constitutional

formulas,

and isomers are

topics of Chapter

XVIII.

PREFACE.
2.

V
which took only a

The treatment

of Valence,

part of a chapter in the first edition, makes up valence table Chapter XI of the revised book.

elements and radicals is given, and the application of valence to the construction of formulas receives special attention.
of the
3. Equilibrium, like valence, has been given a separate chapter. The notions of physical equilibrium, as applied to changes of state and to solution, precede the discussion of chemical and ionic equilib-

common

rium.
4.

The

influence of the several factors in solution

and and
tive

crystallization is brought out in several solubility curves are given.

Chapter VI,

quantita-

table

pounds
5.

solubility for many is inserted in the Appendix.

of

common com-

The chapter on

Acids, Bases,

and

Salts

(XIV)

contains a section on equivalent (normal) solutions. The theory of ionization and electrolysis is given in

Chapter XV.
is ascribed, not to the atomic state of the nascent element, but to the

6.

The " nascent

state

"

presence of catalyzers or excessive amounts of energy.


7.

trial features.

The new book is especially strong in its indusThe following facts illustrate this:

vi
a.

PREFACE.
The methods
of purifying

and softening water are given

in detail.

nitric acids receive

of making hydrochloric and and special illustrations, attention adequate " " as does the contact process for sulphuric acid. c. The applications of the electric furnace and modern elecb.
d.

The commercial methods

trolytic processes are carefully considered.

The

description of the copper, iron,


in a

and

steel

manufacture

is

detailed
e.

and thoroughly modern. Mordants and dyes are treated

fundamental way.

8.

The new book shows that

the properties of the

sulphides form the basis of the Qualitative Analysis of the metals, and the Qualitative grouping is com-

pared with the Periodic Arrangement.


9. The Exercises of the revised text are largely new, and more numerous than in the original edition.

10. The new book has 92 illustrations, as compared with 65 in the older edition. All but 10 of these are from new drawings. Every page of the book has

been

reset.

The
Oliver

reviser wishes to express his thanks to Dr. C. Farrington, of the Field Museum of

Natural History, Chicago, for the photograph of White's Cave (Fig. 64); to the J. T. Baker Chemical

Company,

publishers of The Chemist-Analyst, for the illustrations of the hydrochloric acid and nitric
acid manufacture (Figs. 32

and

50)

and to the United

Gas Improvement Company, Philadelphia, for the " " cut illustrating the making of water gas (Fig. 68).

PREFACE.

vii

About half of the drawings for the new illustrations were made by Miss Margaret C. Hessler. The remainder are the work of Mr. Corry Wilkin, Mr. Barton Westervelt, Mr. Andrew Bolay, and Mr. Claude Postlewait. To all of these the reviser expresses his thanks.
also greatly indebted, and correspondingly grateful, to his colleague, Dr. Eugene C. Woodruff, of the James Millikin Univeris

He

sity,

and

to

Mr.

Steel

Works,

Leslie A. Touzalin, of the Illinois Chicago, for many helpful suggestions


J.

given during the preparation of this revision.


C. H.

JUNE, 1912.

CONTENTS.
CHAPTER
Introduction
I.

PAGE.
1

and Properties. Changes in Substances. Physical and Chemical Physical and Chemical Changes. Matter and Energy. Properties. Reagents and Reactions. Elements and Compounds. Physical States of Matter. Abundance of the Elements. Two Classes of Elements. ImThe Field of Chemistry. Mixtures and Compounds.
Substances
portance of Chemistry.
Exercises.

CHAPTER
. .

II.

Oxygen The Air and Chemical Change. Rusting Priestley and Lavoisier. Burning in the Air.
Oxygen in Air. tory Method.
paring Oxygen.
^Oxidation.

12
of

Metals.

Per Cent of

Common LaboraPreparation of Oxygen. Other Methods of PreCatalytic Action.


Physical Properties.

Combustion.

Deflagration.

Chemical Properties. Energy and

Chemical Change. Flames. The Kindling Temperature. Reversed ComSpontaneous Combustion. Safety Lamp. bustion. Exercises. Importance and Uses of Oxygen.

CHAPTER
Measurement
of

III.

Gases
of

28
Gases, j- Measurement
of

The Volumes
ture; Charles'

Pressure.

Standard Pressure.

Temperature.

Law.

Application of Charles' Law.

Volume and TemperaVolume

and Pressure; Boyle's Law. Application of Boyle's Law. Correction Correction for Both Temperature and Pressure.
Partial Pressure. of the Barometer Reading. Involving Standard Temperature and Pressure.
ix

Problems
Exercises.

CONTENTS.

CHAPTER
Hydrogen
Occurrence.

IV.
PAGE.
?)

*,,'{
Generator.
Igniting

.;..

38
Self-

Laboratory Method

Regulating
cautions
in

of Preparation. Purification of Hydrogen.

Pre-

Hydrogen.

Physical

Properties.

Occlusion of Diffusion, or Transpiration, of Hydrogen. Chemical Properties. Union of Hydrogen and Hydrogen. Use of the Hydrogen Flame. Reduction. Oxygen. Other Methods of Preparing Hydrogen. Uses of Hydrogen.
Exercises.

CHAPTER

V.

.Water

50

Nature of Water. Electrolysis of Water. Synthesis of Relation between the Volumes of HydroWater, by Volume. gen, Oxygen, and Steam. Synthesis of Water, by Weight. Law of Definite Proportions by Weight. Occurrence of Water. Natural Water. Purification of Water. Drinking Water. Filtration. Distillation. Hardness of Water. Boiling. Chemical Properties. Physical Properties of Water. Dissociation of Water by Heat. Action of Metals upon Water. Weight Relations of the Reaction; Hydroxides. Exercises and Problems. Equivalent Weights.

*/

CHAPTER
7

VI.
\/'.

Solution and Crystallization

67
Conditions that Affect

Nature of Solution.
Solubility.

Solubility.

Properties of Solutions. Solubility of Liquids. Saturated and SuSolubility of Gases. Henry's Law. Energy Changes during Solution. persaturated Solutions.

Freezing Mixtures.
'fervescence.

Water

Crystallization. Precipitation and Efof Crystallization, or of Hydration.

Agents.

Efflorescence Decrepitation. Exercises.

and

Deliquescence.

Drying

CONTENTS.

xi

CHAPTER
Fundamental Laws and Theories
Classes of Reactions.

VII.
PAGE.

78

Conservation of Matter.

Multiple Proportions.
Definite Proportions.

The Atomic Theory and

the

Law Law

of of

Proportions.
State.

Explanation of the Law of Multiple Atomic Weights. Atoms and Molecules.

Properties of Molecules.
Exercises.

The MolecutaFTheory and Physical

CHAPTER
Equations and Nomenclature
S3'mbols, Formulas,

VIII.

87

and Equations. Quantitative Meaning of Equations. RadiMultiples of Symbols and Formulas. cals. To Represent Water of CrystalWriting Equations. lization. Calculations from Formulas. Calculations from How a Compound of Two Elements is Named. Equations.
Different

Compounds

of the

Same Two Elements.

Exercises.

CHAPTER
Chlorine

IX.
98

Occurrence.
the

Common Method
Other

of Preparation.

Study

of

Reaction.

Chemical
Chlorine

Properties.

Methods. Action of

Physical Properties. Chlorine and Water.

and

Ammonia.

Chlorine

and

Hydrocarbons.

Uses of Chlorine.

Nascent State.

Exercises.

CHAPTER

X.

108 Hydrogen Chloride and Hydrochloric Acid Occurrence. Commercial Manufacture. Preparation.
Physical
Properties.

Volumetric Composition. Properties. Chlorides. Exercises.

Chemical

xii

CONTENTS.

CHAPTER
Valence

XI.
PAGE.

115
of Valence.

Valence by Standard of Valence. Valences of Some Elements and Radicals. Replacement. Valence of Radicals. Formula Types Based on Valence.

Meaning

Multiple Valence.

Exercises.

CHAPTER
Molecular Weights
Hypothesis.

XII.
121

Combination by Volume; Gay-Lussac's Law. Avogadro's Molecular The Molecules of Elements. GramVapor Density Methods. Weights of Gases. Molecular Weights of Molecular Weight and Volume. Soluble Substances. Boiling Point Freezing Point Method. Methods of Obtaining Exact Method. Osmotic Pressure.
Molecular Weights.
Exercises.

CHAPTER
Atomic Weights Determination

XIII.
133

Atomic Weight Defined. of Atomic Weights. Summary of the Method. Accuracy of the Method. Application of Atomic Weight Dulong and Petit's Rule. Exercises. Methods.

CHAPTER
.Acids, Bases,

XIV.
142

and Salts
Anhydrides.
Bases.
Alkalies.

Acids.
tion.

Neutraliza-

Two

Classes of Oxides.

Action of Oxides with Acids

Basic Salts. Acid Salts. Salts. and Bases. Basicity and Acidity. Equivalent Solutions of Acids, Bases, and Salts. Exercises. Nomenclature of Acids, Bases, and Salts.

CONTENTS.

xiii

CHAPTER XV.
PAGE.

lonization

155

Double Decomposition of Acids, Bases, and Salts. The Electric Conductance of Freezing Points, Etc., of Solutions.
Solutions.

tion of Neutralization.

ExplanaDegree of lonization. Test Reactions are Ionic. Replacement of Oxidation and Reduction Ions; the Electromotive Series.

Theory

of Dissociation in Solution.

Heat

of Neutralization.

of Ions.

Electrolysis of Acids, Bases,


1

and

Salts.

Electro-

Chemical Equivalents.

Hydrolysis

Exercises.

CHAPTER
Nitrogen and the Atmosphere

XVI.
169

Nitrogen. Preparation. Properties. " " a Mixture. Character of the AtAtmospheric Nitrogen Helium. Carbon Dioxide in the AtArgon. mosphere.

Occurrence

of

Water Vapor in the Atmosphere. mosphere. Atmospheric Dust. Weight and Pressure of the Atmosphere. Liquefaction of Air. Determination of the Properties of Liquid Air. Air a Physical Mixture. Proportion of Oxygen in Air.
Exercises.

CHAPTER
^ Ammonia
Occurrence.
Nitrides.
erties.

XVII.
183

Laboratory Preparation.
of

Preparation from

Commercial Sources
Liquefaction

of Ammonia. Physical PropAmmonia. Liquid Ammonia as

a Refrigerating Agent. Chemical Properties. Ammonium Ammonium Salts. Dissociation of Ammonium Hydroxide. Compounds. Composition of Ammonia. Synthesis of Ammonia. Action of Chlorine on Ammonia. Exercises.

XIV

CONTENTS.

CHAPTER

XVIII.
PAGE.

Molecular Formulas and Equations Molecular Equations. Determination


Constitutional Formulas.

195
of

Formula.
Exercises.

Polymers.

Isomers.

/
j

CHAPTER XIX.
202
Preparation. laboratory Method. Preparation Compared with that of Hydrochloric Acid. Action upon Metals. Properties of Nitric Acid. Oxidation by Nitric Acid. Aqua Regia. Nitrates. Sources of Nitrates. Uses of Nitric Acid and the Nitrates.
Nitric

Nitrogen Acids and Oxides


Acid.

Commercial

Nitrous Acid. Nitrogen Pentoxide. Nitrogen Trioxide. Nitric Oxide. Nitrogen Dioxide and Nitrogen Tetroxide. Nitrous Oxide. Exercises. Hyponitrous Acid.

CHAPTER XX.
Equilibrium and

Mass

Action

219

Chemical EquilibEquilibrium. Physical Equilibrium. rium. Reversible Reactions. Ionic Equilibrium. Chemical Equilibrium in Solution.

Mass

Action.

Exercises.

CHAPTER
Sulphur and
Its

XXI.
227
Physical ProperUses. Sulphur

Compounds

Occurrence and Preparation of Sulphur. Chemical Properties. ties; Allotropism.

Compounds.
sulphides.

Hydrogen

Sulphide.

Sulphides.

Hydro-

Acid.
Acid.

Sulphur Sulphur Trioxide.

Carbon Disulphide. Precipitation of Sulphides. Dioxide. Chemical Properties. Sulphurous


Contact Process for Sulphuric
Purification of Sulphuric Acid. Acid. Its Reduction. Uses.
of Stability Sulphates. Exercises.

Chamber
of

Process.

Properties Sulphates.

Sulphuric

Acid

Sulphates.

Test for Sulphates.

Thiosulphates.

CONTENTS.

XV
PAGE.

CHAPTER
Carbon and
Its

XXII.
i

^r Compounds Occurrence. The Diamond.

-? v'

.-V

-.

252

Graphite.

Carbon. Carbon.
tion.

Coal.

Charcoal.
Charcoal.

Lamp-black.

Amorphous Coke and Gas


Prepara-

Animal

Carbon Dioxide.
Chemical

Physical Properties. mentation. Baking Powders.


to
Life. Carbonic Natural Carbonates.

FerProperties. Relation of Carbon Dioxide


Bicarbonates.

Acid.

Carbonates.

Laboratory Preparation. Properties. Cyanogen. Hydrocyanic Acid. Methane. Ethane. Compounds of Carbon and Hydrogen. Ethylene. Acetylene. Illuminating Gas. Preparation

Carbon Monoxide.

by

Distillation of

Coal.
of Gas.

of the

Two Kinds

Water-Gas Process. Comparison Pintsch and Producer Gases.

Exercises.

CHAPTER
Flames, Light, and Heat

XXIII.
281

Luminosity
Power.
pipe.
of

of

Flames.

Structure

of

Flames.

Non-

Luminous Flames.

Heat and Light of Flames. Candle Mouth BlowOxidizing and Reducing Flames. Sources of Heat. Furnaces. Thermite. Smoke.

Heat Energy Changes Accompany Chemical Changes. Formation and of Decomposition. Exothermic and Endothermic Reactions. Heat of Formation Evolved in Stages.
Exercises.

CHAPTER XXIV.
Fluorine, Bromine, Iodine,

and Their Compounds


Properties.

294
Acid.

Halogens.

Fluorine.

Hydrofluoric

Bromine; Preparation and Properties. Hydrobromic Acid. Occurrence and Preparation of Iodine. Properties. Hydriodic Acid. Compounds of Halogens and Oxygen. Compounds of Halogens with Oxygen and Hydrogen. Hypochlorous Acid. Chlorous Acid. Perchloric Chloric Acid. Acid. Compounds of Bromine with Oxygen and Hydrogen.
Iodine Compounds.

The Halogen Family.

Exercises.

XVI

CONTENTS.

CHAPTER XXV.
->

Ozone and Hydrogen Peroxide


Ozone.

PAGE 312
Peroxide.
Properties

and Composition.

Properties. Hydrogen Exercises.

CHAPTER XXVI.
~The Nitrogen Family ./?' Occurrence and Preparation
.

.*

319
Properties.

Red

Phosphorus. Matches. Hydrogen

of Phosphorus. Molecular Weight of

Phosphorus.
Salts.

Phosphide.

of Phos Phosphorus Oxides. phorus. Hypophosphorous Acid. Phosphorous Acid. Uses of Phosphates; FerPhosphoric Acids. Phosphates. tilizers. Arsenic, Occurrence, Preparation and Properties. Marsh's Test. Arsenic Trioxide. Hydrogen Arsenide.

Phosphides.

Phosphonium Oxygen Acids

Arsenious Acid.
Trisulphide.

Arsenic Greens.

Arsenic Acid.

Arsenic

Antimony; Preparation and Uses of Antimony. Properties. Antimony Compounds. Bismuth Salts. Bismuth; Preparation and Properties. The Nitrogen Family. Uses of Bismuth. Exercises.
Sulpharsenites.

CHAPTER
The
Periodic System

XXVII.
346

Natural

Families.

The

Periodic

Properties of Regularities. " " Gaps in the Arrangement.

an

Arrangement and Its Element Determined.

Prediction of

Unknown

Ele-

ments.
clusion.

The

Periodic Table.

The Argon Family.

Con-

Exercises.

CHAPTER
Silicon

XXVIII.
356
Silicon.

and Boron
Occurrence and Preparation of
Silicon Carbide.
Silicon
Silicic

Compounds.
Sili-

Silicon Dioxide.

Acids.

cates.

Glass.

Boric Acid.

Boron. Preparation Borax. Exercises.

and

Properties.

CONTENTS.

Xvii

CHAPTER XXIX.
PAGE.

Metals

366

Metals and Non-Metals.


Metals.
Series.

Alloys.

Occurrence and Extraction of Classification of Metals. Electromotive


of the Metals.

Compounds

Exercises.

CHAPTER XXX.
The
Alkali

Metals
Lithium.

374

Sodium; Preparation and Sodium Oxides and Hydroxide. Properties. Soap. Sodium Carbonate. LeBlanc Process. Solvay Process.
General Properties.

Sodium Phosphate. Sodium Bicarbonate. ride. Sodium Nitrate. Other Sodium Salts.
Stassfurt Deposits.

Sodium ChloPotassium.

Potassium Oxides. Potassium Hydroxide. PoPotassium Carbonate. Potassium Chlorate. tassium Bromide and Iodide. Potassium Sulphates. Other Potassium Salts. Ammonium Salts. Exercises.

CHAPTER XXXI.
Alkaline-Earth Metals

392

Calcium. Calcium Oxide. Calcium Group. Calcium Chloride. Calcium Carbonate. CalHydroxide. Calcium Phosphate. cium_Sulphate. Softening of Water. Other Calcium Salts. Mortar, Cement, and Concrete. Strontium. Barium. Magnesium and Its Compounds.

The

Radium.

Exercises.

CHAPTER XXXII.
Zinc,

407 Cadmium, and Mercury Zinc The Zinc Group. Zinc; Its Properties and Uses. Its Cadmium. Properties and Mercury; Compounds. Exercises. Uses. Mercury Compounds.

xviii

CONTENTS.

CHAPTER
Copper, Silver, and Gold

XXXIII.
PAGE.

414

Relation of Group to Alkali Metals.


lurgy of Copper.
Refining.

Occurrence and Metal-

Properties and Uses.


Silver.

Copper
from
of

Compounds.
Its Ores.
Silver.

Copper-Plating.

Extraction
of

Properties and Uses of Silver. Gold. Photography. Metallurgy


Exercises.

Compounds
Gold.

Properties and Uses.

CHAPTER XXXIV.
Aluminum
".

428

Its Preparation. Occurrence of Aluminum. Properties. Aluminum Oxide and Hydroxide. Uses. Uses of Aluminum Hydroxide. Mordants. Aluminum Salts. Dyes. Alums. Porcelain and Stoneware. Exercises.

CHAPTER XXXV.
Iron,

Cobalt, and Nickel

436
Its Metallurgy.

Occurrence of Iron.

Cast Iron. Bessemer Steel Alloys. Process. Crucible and Cementation Steel. Causes of the Behavior of Iron and Tempering of Steel. Nickel and Steel. Iron Compounds. Properties of Iron. Exercises. Its Compounds. Cobalt and Its Compounds.
Iron. leable

Commercial
Iron.

Steel.

The Blast Furnace. MalWrought Iron. Process. Open Hearth

CHAPTER XXXVI.
Manganese and Chromium
455
Its Oxides, Hydroxides, and Salts. PreparaManganese. tion and Properties of Manganates and Permanganates. Chromium. Oxidation by Manganates and Permanganates. Chromous and Chromic Compounds. Chromium Trioxide Oxidaand Chromic Acid. Chromates and Dichromates. tion by Chromates and Dichromates. Exercises.

CONTENTS.

Xlx

CHAPTER XXXVII.
PAGE.

Lead, Tin, and Platinum


Occurrence and Preparation of Lead. of Lead. Lead Compounds. Tin;
Preparation.
Its Properties

467
Properties and Uses
Its

and Uses.

Platinum.
Uses.

Occurrence

and

Occurrence and Tin Compounds. Properties and Preparation.

Chlorplatinic Acid.

Exercises.

CHAPTER XXXVIII.
Some Carbon Compounds
Organic
Chemistry.
Classes
of

479

Hydrocarbons of Marsh Gas Series. Series. Benzene Hydrocarbons.


Gas.
hydes.
Alcohols.

Carbon Compounds. Ethylene and Acetylene Petroleum and Natural


Ethers.

Liquors.

Glycerine.

Alde-

Acetic and Halogen Derivatives of Hydrocarbons. Formic Acids. Other Acids. Esters. Fats Vinegar. and Oils; Soaps. Amines and Alkaloids. Carbohydrates.
Sugars.
Cellulose.
its

sides.

Phenol and

Starch. Paper. Derivatives,

Bread.

Gluco-

CHEMISTRY.
CHAPTER
I.

INTRODUCTION.
1.

Substances and Properties.

Chemistry

may

be defined as the science that deals with substances

and the changes they undergo. We distinguish between substances by then* characteristics, or qualiThus, a diamond has greater hardness, or scratching power, than glass, and a silver coin gives " " a distinct when thrown upon a table, while ring " a lead coin falls with a thud." The characterties.

istics

of substances are called properties. Among the properties of a substance are its odor, taste,

temperature, boiling temperature, or ability inability to dissolve, burn, etc.


color,
2.

melting

Changes

in Substances.

The changes

that

substances undergo may be the so-called natural changes, such as the freezing of water, the fermenting
of fruit juices, and the rusting of iron, or they may be brought about by man, such as the extraction of

lead from

its ore,

the magnetizing of iron, the dis-

2
tillation of water,

INTRODUCTION.

In every one of these cases we know that there has been a change because some of the properties of the substance obtained are different from those of the substance taken. The boiled water is changed to a
of coal.

and the burning

steam; the magnetized iron vapor can attract other objects of iron or steel; the fercolorless, light

mented
tation.

fruit juice contains

new

substances,

e.

g. ?

alcohol, acetic acid, etc.,

not present before fermen-

The changes Physical and Chemical Changes. given in 2 (and all others) maybe divided into two
3.

classes:
(1) (2)

Physical changes.

Chemical changes.
the
first class
is

belong those changes in which not permanently altered, but regains A physical after the change. its original properties with the be same subrepeated change may usually stance. Illustrations are: the magnetization of a
the substance
knife blade, the production of light by the incandescence of carbon (electric light), the melting of ice, and the boiling away of water.

To

Chemical changes, on the other hand, involve a permanent alteration in the substance. Thus, burnt magnesium does not revert to magnesium when
rusted iron has lost the properties of iron; the carbon dioxide produced when coal is burned is
cooled;

REAGENTS AND REACTIONS.

neither carbon nor oxygen, although these substances united to produce it.

Just as Physical and Chemical Properties. divide changes into physical and chemical changes, so we classify the properties of substances as either
4.

we

Those properties physical or chemical properties. are physical that can be determined without a chemical

change.

Such

are

the

boiling

temperature,

melting temperature, specific gravity, taste, odor, etc. Chemical properties can be shown only by a
chemical change.

The
it

shown by burning

combustibility of sulphur a chemical change.

is

described in Chemistry, its most important physical as well as chemical properties are given. In fact, our most common method
is

When

a substance

of telling that

a chemical change has taken place

is

to note the changes in the physical properties of the substances used. Thus, when mercuric chloride and

potassium
together in
obtained.

iodide,

two white

solids,

are

ground

a mortar, a bright scarlet powder is The change of color, alone, suggests that

some new substance has been formed.


Substances which 5. Reagents and Reactions. have a chemical effect upon one another are said to react, and a chemical change is therefore called a reaction. The substances which react are called The substances formed are the reagents, or factors.

INTRODUCTION.

products. Thus, when copper is treated with concentrated nitric acid, a chemical reaction takes place, and the copper and the nitric acid are the reagents (or
factors).

The brown gas formed

is

one of several

" " is often applied to subadjective reagent stances in the form in which they are commonly " " used in the laboratory. Thus ammonia reagent

products.

The

means an aqueous
itself
is

solution of

ammonia; ammonia
" "

a gas. Similarly, by sodium reagent we mean the solution of solid sodium hydroxide in water. hydroxide
6.

Matter and Energy.


.

may

Substances are the kinds of matter (cf. Matter itself 1) be defined as that which occupies space, or takes up room.
also has weight, that
is,

Matter
gravity.

it

attracts

other matter.
is

The
called

earth's attraction for matter at or near its surface

of a body is the quantity of matter in it. At a given the mass of a body is measured by its weight. The weight may change as the earth's attraction for the body changes. Thus, bodies weigh most at the earth's surface and at its poles.
place,

The mass

The mass, of course, remains the same everywhere. The density of a substance is the mass of it in
Thus,
1 c.c. (cf.

unit volume.

Appendix
7.8.

i)

of iron weighs 7.8 grams; iron has,


of a substance is

therefore,

a density of

specific gravity, or relative density, obtained by dividing the weight of a given

The

stance
stance.

by the weight of the same volume of For liquids and solids the standard
71).

volume of the subsome standard subis

pure water at

C.

(cf.

PHYSICAL STATES OF MATTER.


Specific

Gravity

Weight
Weight
is

of equal

of body __ volume of water


(cf.

For gases the standard

air or

hydrogen

51).

A third property of matter is inertia, or helplessEnergy. Matter cannot move itself if at rest, nor stop itself if moving, nor change the velocity or direction of its motion. Anything that can produce changes in the motion of matter is called a force. Gravity, steam, and the wind are forces. Matter under the influence of a force can do work upon other matter, " and is said to possess energy." Thus, falling water drives a air in motion drives mill-wheel; it has energy. The wind a windmill or a ship. Steam engines run because of the expansion motion of steam. These are all examples of physical forces. Coal also possesses energy chemical energy. When it burns (a chemical change) heat is liberated, and this heat can generate steam to run an engine or a dynamo (cf. 27).
ness.

7.

Physical States of Matter.

Matter

may

exist

in the solid, liquid, and gaseous condition. Thus, water is known as ice, liquid water, and steam. The
air is

commonly a
(cf.

gas,

but

it

may

be liquefied and
is

even frozen
gases.

197).

The same

true of other

In the solid state a substance has a definite form, but this is not true of liquids and gases. Liquids have definite volumes, but they take their form from the vessel holding them. Gaseous bodies are without form or volume of their own. When they are put into a vessel they spread in all directions and fill
completely. Although changes of physical state are accompanied by decided alterations of properit

6
ties,

INTRODUCTION.
they are called physical changes and not chemiwe can reverse them by restoring the

cal

changes;

original conditions.

Elements and Compounds. Almost all substances may be shown to consist of two or more different substances, and are therefore called compound substances, or compounds. There are, however, between seventy and eighty substances which
8.

we

are unable to decompose, with our present methThe thousands of ods; these are called elements.

small

compounds known are made up of this relatively number of elements. Less than half of the

elements are ever found free in nature; the others occur only as parts of compounds, and must be

A list

separated from combination by chemical processes. of the elements is given in Appendix iii.

Two

Classes of Elements.

The elements

are

generally divided into two classes: metals and nonmetals. There are important physical differences

between the two

classes.

Thus, the metals have a

peculiar luster, they are malleable, ductile, etc., while the non-metals lack these properties. All

metals are solids under ordinary conditions except mercury. Some of the non-metals are solids, like

phosphorus and sulphur, or gases,


chlorine.

like

oxygen and
differ-

Bromine

is

a liquid.

The
(cf.

chemical

ences are also very important

161).

MIXTURES AND COMPOUNDS.


9.

Abundance

of the

Elements.

Not

half of the eleall

ments are at
F.

com-

mon; many are very rare.

W.

Clarke has

made

an estimate of their abundance (see following


table).
is

The

solid crust

assumed to make up
of the earth;

93%

the

ocean, about 7%, and the atmosphere, 0.03%.

Fiu.

1.

ELEMENT.

INTRODUCTION.

" mixture." The rock, granite, is a guish it from mixture of minerals. The glassy quartz, flaky mica, and pink or white feldspar can readily be distina black be may picked out by mechanical means, and no chemical change Most rocks and soils is required to separate them.
guished in
it.

Sometimes there

is

also

ingredient, hornblende.

All of these

are mixtures, as granite is, of several ingredients. The constituents of granite, just named, are all may also have mixtures of elements. compounds.

We

grind iron and sulphur together in a mortar, 7 using grams of iron for every 4 of sulphur, we get a mixture the color of which is a blend of the colors
If

we

of the

are

two elements. mixed with great

Even though
care, the

the materials

microscope reveals

side

the unchanged particles of iron and sulphur lying by side. A magnet still attracts the iron.

We

can separate the iron and sulphur most conveniently This disliquid, carbon disulphide. If the mixture solves the sulphur, but not the iron. of carbon disulphide, sulphur, and iron is poured upon a filter, the filtrate (what passes through) conThe residue sists of carbon disulphide and sulphur. upon the filter paper is the iron. When the carbon disulphide is allowed to evaporate, the sulphur remains. The elements mixed in the mortar were separated by a physical operation; they had not united to form a compound. If some of the mixture of iron and sulphur is

by using the

THE FIELD OF CHEMISTRY.


heated, a chemical reaction is started. becomes very hot, and glows brightly.

The mass

When

the

product of the reaction is examined,

it is

found to

be neither iron nor sulphur, as judged by its propThe magnet does not attract it. Carbon erties. disulphide does not dissolve the sulphur. The iron and sulphur have united to form a compound, ferrous sulphide (cf. 106). They might have been in any proportion to form a mixground together ture,.but to form ferrous sulphide they unite in the proportion of 7 parts, by weight, of iron to 4 parts of Any excess of either would simply be left sulphur. uncombined. over, We may summarize the differences between mixtures

and compounds thus:

1.

portion.

In a mixture the ingredients may be present in any proIn a compound the elements are united in definite
(cf.

proportions
2.

65).
is

When

a mixture of elements

energy change.
of heat
3.

The formation

of a
i.

made there is generally no compound is usually acevolution or absorption

companied by an energy change,


(cf.

e.,

27).

ingredients of a mixture may be separated by mechanical means. The elements of a compound can be separated only

The

by some chemical change. Mixtures are sometimes


mixtures.

called

physical,

or

mechanical,

Both Physics and Field of Chemistry. deal matter and But with its changes. Chemistry
ii.

The

10

INTRODUCTION.

Physics considers especially the changes in which the composition of the substance is not altered, while

Chemistry
substances.

is

concerned with those that result in new The study of substances and their

is thus the particular field of Chemistry. occur in the earth, but many others substances Many must be made in the laboratory, or on a commercial

properties

scale.
ties of

But the occurrence, preparation, and properelements and compounds are only a part of
in Chemistry.

what we study

There are

rules ac-

cording to which substances react; these are the To explain 65 and 94). Laws of Chemistry (cf. a rule or law we devise a theory, or hypothesis (cf.

95 and 141).

A knowledge of Importance of Chemistry. Chemical Science is necessary for the intelligent study of other natural sciences, such as geology,
12.

astronomy,
sciences

biology,

physiology,

etc.,

for

these

make

Chemistry.

special applications of the ideas of Chemistry is also very practical, for


it

the facts and methods

teaches are in the most


life.

common

use in the arts and in every-day

It

finds application in medicine, in sanitation, in domestic science, in the extraction of metals from their
ores, in the refining of

petroleum and coal


steel,

tar,

and

in the
gas,

manufacture of
dyestuffs,

illuminating and fuel


ice,

paints,

food products,

alcohol,

soap, glass, paper, explosives, etc.

EXERCISES.
13. Exercises.

11

the following as either physical or chemical the changes souring of milk, the burning of wood, the evaporating of water, the tarnishing of silver, the dissolving of sugar in
1.

Classify
:

water, the bleaching of muslin, the melting of lead.


2.

Give

all

the physical properties you

know
ir,on,

of the following

substances:
3. 4.
5.

lead., wood, sugar, coal, gojd, Give the chemical properties of the substances of 2. What reason is there for considering silver an element?

Name some

electricity, of light,

physical changes brought about by means of and of heat. Name some chemical changes

brought about by the same agents. 6. Learn the metric tables for length, volume, and weight (Appendix i). In 1 c.dm.? 7. How many cubic centimeters in a liter?
State the relation between
cm., dm.,
g.,

mg., dg.,

eg., kg.

Between mm.,
and

and m. 8. In what way are the metric units volume connected?


9.

of length, weight,

What

is

the weight of 106

c.c.

of water?

in

c.c.,

of 30 g. water.

Of 30

g.

platinum of S.G.

Give the volume, 21.5. Of 30 g.

ether of S.G. 0.72.

CHAPTER
OXYGEN.
14.

II.

The

Air and Chemical Change.


difficult to handle,
it is

Since air

is

a gas, and hence


in learning

men were

slow

connected with the important chemical changes that take place only when it is Among these changes are the respiration present. of animals and plants, the fermenting of fruit juices,
the
(cf.

how

decay

of

wood and
substances.

other

25), the tarnishing of metals,

organic materials and the burning

of combustible
air to these

When

the relation of

of

changes was once recognized, the progress science was rapid.

15.

Rusting of Metals.
temperatures.

Most metals undergo

tarnishing, or rusting, either at ordinary or at ele-

had been known for many centuries, but it was Jean Rey who first noticed, in 1630, that given amounts of the metals increase in weight when the metals rust, and who first stated that contact of the metal with air was
vated
This
the probable cause.

Other investigations led to the

same

However, Rey's explanation of not was rusting accepted and applied until restated
12

conclusion.

PRIESTLEY AND LAVOISIER.

13

by

Lavoisier, in

1774.

quantity of tin in

Lavoisier sealed a weighed flask, and heated it for several

He noticed that the tin was partly changed days. into the white powder which had been studied by
Rey.
occurred inside the

Although a chemical change had evidently flask, no change in weight could

be noticed.

was opened, a certain amount This showed that the tin rusted by taking up something from the air in
flask

But when the

of air rushed in.

the flask.

In the same year Priestley and Lavoisier. in which Lavoisier made his important experiment with tin, Priestley, in England, prepared the gas
1 6.

which

tin

and other

metals take up from the air. Priestley


filled

glass

vessel

(Fig. 2)

with mercury
various

and

floated

substances to the top of the mercury. He

means
glass.

then heated them by of a burning

stances

One of the subwas the red

ide.

powder, mercuric oxIt can be made


Flo
.

by heating mercury

2.

14

OXYGEN.
at

for a long time, in the air, just below the boiling point of

a temperature
C.}.

mercury (357

By heating mercuric oxide Priestley obtained oxygen, a colorless gas which supported burning better than air, and which could be breathed without harm
by mice.
" Priestley called the gas good air." The date of the discovery of oxygen was August 1, 1774.

Lavoisier, with his

recent experiments in mind, concluded that the gas Priestley had discovered was the very constituent of the air that caused the rusting
of metals.

own

So Lavoisier devised the following ex-

periment

(Fi^. 3):

retort containing

some mercury was

in

communication

with a bell-jar the mouth of which was closed bty mercury. There was thus an enclosed quantity of air in the retort and belljar.

The mercury
the
retort
in
this

of

was
for

heated

contact
air

with

twelve days. As the


heating continued, the surface of the

mercury became
covered with the red
FIG
3.

powder, and the air diminished to about


four
fifths

of

the
or

original volume.

The

gas remaining no longer supported

life

burning. It was, in fact, nitrogen (cf. it is a constituent of niter, or saltpeter.

186), so called because

When

Lavoisier removed the red powder from the mercury,

BURNING IN THE
and heated
"
it,

AIR.

15

it

good volume
"
i.

air."
lost

The volume
by the
air.

was broken up into mercury and Priestley's of this gas was just equal to the
Lavoisier

named

the
it

new gas oxygen,


in all

e.,

acid-former," because he thought

was present

acids.

Scheele (ShEla), a Swedish chemist, undoubtedly prepared

oxygen
later.

in 1771-1773,

He

obtained

it

but his results were not published until from manganese dioxide, from niter, and

from mercuric oxide.

When metals unite with Burning in the Air. are solids and readily the (oxides) products oxygen handled. But when ordinary combustibles, such as wood, wax, and illuminating gas, are burned, the products are gaseous and escape observation. Yet
17.
;

the chemical change

is

essentially the

same as

in

the rusting of metals: it is the union of the substances burned with the oxygen of the air.

FIG.

4.

The apparatus
formed
in the

of Fig. 4 enables us to prove that the products burning of a candle weigh more than the candle.

16
The
flask,

OXYGEN.
connecting tubes, on the balance.
etc.,

and

straight drying tube (B)


is

are weighed

The candle

then lighted, the

stopper replaced in the flask, and the U-tube (A) is attached. Air is now drawn through the apparatus by a suction pump.

The

candle should continue to burn.

The tube

(B) contains

sodium hydroxide and calcium chloride to catch the products (carbon dioxide and water) formed as the candle burns. The U-tube also contains sodium hydroxide and calcium chloride to remove any carbon dioxide or water from the air. Although the
candle wastes away, the apparatus gains in weight because of the oxygen taken from the air.

1 8.

of

Per Cent of Oxygen in Air. -- The experiment Lavoisier showed ( 16) that air is about one fifth

careful experiments confirm Lavoisier's conclusion. Instead of heated mer-

oxygen, by volume.

More

cury, yellow phosphorus

may be
The
is

used at the ordinary


shrink in

temperature (Fig.

5).

air ceases to

volume when
removed.

practically

21%

has been

The gen. to form phosphorus pentoxide, a white solid that dissolves readily in water.
The oxy19. Preparation of Oxygen. gen used in the laboratory is usually obtained by heating potassium chlorate to 350-400 C. Potassium chlorate is 39.18%
oxygen, by weight, and
FIG.
5.

the volume of the oxyphosphorus and oxygen unite

This

all

the oxygen
is

is

given

off

if

sufficient

heat

applied.

[COMMON LABORATORY METHOD.

17

332 for the intermediate formation (See, however, of potassium per chlorate.) Potassium chloride is not volatile at the temperature used and remains
behind.
Potassium chlorate potassium chloride

oxygen.

Composed
of

potassium,
chlorine,

Com.

>
<
J

<
(

potassium,
,
.

posed
of

chlorine,

oxygen.

20.

Common

Laboratory

Method.

Oxygen

is

produced much more easily, and at about 200 C., if we heat, not potassium chlorate alone, but potas-

sium chlorate mixed with manganese dioxide, or


with
ferric

oxide.
6).

This

is

the
is

method

(Fig.

The gas

laboratory collected in bottles

common

FIG.

6.

filled

also,

with water and inverted in a water pan pneumatic trough).

(called,

In the decomposition of potassium chlorate, as in all chemical reactions, there is a definite relation be-

18

OXYGEN.
of the substances

tween the weights


those formed
Since
(cf.

taken and of
65).

Law

of Definite Proportions,
is

oxygen, and all of it is liberated, we can always calculate that 100 grams of potassium chlorate will give 60.82 grams of potassium chloride and 39.18 grams of

39.18%

of potassium chlorate

oxygen.
21. Catalytic
(or ferric oxide)

Action.

--The manganese

dioxide

used to increase the speed of de-

composition of potassium chlorate is not permanently changed in the experiment, but may all be recovered.

substance which affects a reaction merely by its presence, without itself being used up, is called a
catalytic, or contact, agent,

and the action

is

called

catalysis, or contact action.

22.

Other Methods.

Other methods of prepar-

ing oxygen are:


(1)

Decomposition of water by the

electric current

57 the
16).

and

61).

(2)

historic

Decomposition of mercuric oxide by heat. This method of Scheele, Priestley, and Lavoisier
is

is
(

Mercuric oxide
(3)

7.41% oxygen, by weight.


Barium peroxide
is is

Decomposition of barium peroxide.

a white solid that

18.9% oxygen.

It gives

up half of its oxygen

when heated, and barium monoxide remains. > barium monoxide + oxygen. Barium peroxide A commercial method of preparing oxygen (Brin's
is

process)

to heat barium monoxide to about 700

C., at increased pres-

CHEMICAL PROPERTIES.
sure, in

19

a current of air. The barium monoxide and oxygen barium peroxide. The air current is then cut off and the pressure lowered. As a result the barium peroxide is decomposed into barium monoxide and oxygen. The oxygen is
unite, giving

collected

and

stored.

and the

air current is

reverse change again takes place.


(4)

the pressure is raised once more, passed over the barium monoxide, the combination of barium monoxide and oxygen

When

oxide
of
it.

is

Decomposition of manganese dioxide. Manganese di36.9% oxygen. At about 600 C. it gives off one third

Manganous-manganic oxide remains.


is

Manganese
(cf.

di-

oxide

found in nature as the mineral pyrolusite

500).

23. Physical Properties. less, tasteless,, and odorless.

Pure oxygen

is

color-

It is somewhat heavier and 16 times as heavy as hydrogen (cf. One liter of it weighs 1.429 grams at C. 51). and 760 mm. pressure (cf. Appendix v). About

than

air,

c.c. of

oxygen dissolve in 100


(cf.

c.c.

of

water under

ordinary conditions

83).

Gaseous oxygen may be condensed at 118 C. i. 50 and 50 atmospheres pressure 760 mm. X e.,
(cf.

36), to a bright blue liquid

having magnetic

properties.

This

may

be

solidified.

The chief chemical Chemical Properties. of of is its uniting with other oxygen property power elements to form oxides. This property is shown in the rusting and tarnishing of the metals (cf. 15), and in the energetic way in which combustibles burn
24.

20

OXYGEN.

in oxygen. Thus, a pine splinter which is merely glowing in the air will burst into flame if put into

oxygen. Burning in the air is more slow because the oxygen is diluted with inert gases (chiefly nitro186 and 190) which do not support ordigen, cf.

nary burning at
iron oxide
in air,
(cf.

all.

brilliant scintillation,

Iron burns in oxygen with forming a black solid, magnetic


charcoal burns with a glow, as

492)

brightly; calcium, magnesium, phosphorus, and sulphur burn with intensely brilliant flames to give calcium oxide (quicklime),
oxide,

but

much more

phosphorus pentoxide, and sulphur dioxide, respectively. Calcium oxide, magnesium oxide, and phosphorus pentoxide are white solids. Sulphur dioxide and carbon dioxide are colorless gases. Sulphur dioxide has the characteristic odor of burning sulphur. Many of the elements are found in nature as oxides. Water is hydrogen oxide. 317 and Fluorine and the argon family alone (cf. 191) form no oxygen compounds.

magnesium

the union of oxygen with other substances, whether elements or compounds, we give the name oxidation. The substance that com25. Oxidation.

--To

bines with oxygen is said to be oxidized. stance that gives up its oxygen to another

A
is

sub-

called

an oxidizing agent. Potassium nitrate is an oxidizing 232) of potasGunpowder, a mixture (cf. agent. sium nitrate, charcoal, and sulphur, owes its rapid

COMBUSTION.

21

reaction (explosion) to the fact that the potassium nitrate oxidizes the charcoal and sulphur. Oxidation may be rapid, or it may be slow. Thus,

magnesium may burn up rapidly in oxygen, giving magnesium oxide ( 24) and, besides, much heat and light, or it may be changed slowly (rust), when exposed to moist air, into the same product,
a piece of

without evolution of light and, apparently, without Yet the energy set free in the liberation of heat. one case is the same as in the other. There is no perceptible rise of temperature in the slow oxidation
because the heat
free.
is

dispersed as rapidly as
is

it is set

Decay, as of wood,
the rusting of iron.

a form of slow oxidation;

so

Decay takes place only in the presence of certain oxidizing bacteria (cf. 230).
is

Burning, or combustion, in air simply rapid oxidation ( 17). The phenomena of heat and light accompany combustion because energy is given off much more rapidly than it can be
26. Combustion.
is

dispersed. As a result the burning body becomes hot. The products of combustion are chiefly oxides. Because a combustion started in air continues in

oxygen, oxygen
bustion.

is

said to be a supporter of com-

Combustion

in air or

oxygen

is

not different from

any other chemical union producing heat and light, such as the case of iron and sulphur (cf. 10). Other
gases

may

be supporters of combustion just as truly

22
as
(cf.

OXYGEN.
oxygen.
118).

Thus,

phosphorus burns in chlorine

Deflagration is very rapid combustion, such as that of gunpowder. When charcoal and sulphur burn in the air or oxygen, the oxidation takes place at the surface, where the oxygen is in
contact with the combustible. But in gunpowder (cf. 25) the oxygen (contained in the potassium nitrate) is so close to every
part of the combustibles that the oxidation takes place almost In an enclosed space, the instantly through the whole mixture.

When released, they gases formed are under great pressure. are capable of hurling a projectile, or of tearing apart masses of
rock.

27.

Energy and Chemical Change.

In

it

was

stated that coal has chemical energy, because heat is liberated when it is burned. The same is true for

Not only
this

the other combustibles described in this chapter. in oxidation, but in many other chemical
is

changes, heat

given

off (cf.

10).

Whence comes
or

energy?

We

must assume that a substance (element

compound)

consists not only of matter, but also of

energy associated with the matter. Carbon is not only the carbon matter, but the matter plus energy.

Oxygen, as we know

it,

is

the elementary material

and energy. When carbon and oxygen unite, the resulting compound, carbon dioxide, cannot hold all the energy originally associated with its two conSimilar stituents, hence some energy is set free.
reasoning applies in other cases.

KINDLING TEMPERATURE.

23

The compounds
tion of

that are formed with the evoluare very stable,


i.

much energy

e.,

they are

decomposed with difficulty. Thus, water and carbon dioxide are very stable compounds (cf. 311).
28. Flames. A flame is a gas in combustion. To burn with a flame a substance must either be gaseous, itself, or
it must evolve gaseous combustibles. Magnesium, sulphur, phosphorus, and wax burn with

flames because they are

first

converted into the

gaseous form; wood and

soft coal,

because they give

off combustible gases (cf. illuminating gas, 297); but charcoal and coke, which contain practically no

volatile constituents,

merely glow.

- - The temperature at which a combustible begins to burn is called its


29. Kindling Temperature.
ignition, temperature. Thus, yellow phosphorus ignites at about 40 C., in air, and sulphur at about 260 C. The heat given off in the burning of one part of a substance raises the tem-

kindling,

or

perature of adjacent parts to the ignition point, as in the burning of wood, paper, etc. In the match
the head

by

is ignited by friction, and the heat generated the burning of the head ignites the wood.

at, or above, the kindling or will candle burning in an combustion cease. temperature, enclosed portion of air goes out when the oxygen falls below 17%. With so little oxygen present, heat is not evolved rapidly enough

The burning body must be kept

to maintain the ignition temperature.

But with phosphorus

24
the heat evolution
is

OXYGEN.
is more rapid, and the product of combustion 24) which does not dilute the oxygen remaining,

a solid

(cf.

hence burning goes on until all the oxygen is used up. A moderate draft of air is favorable to combustion, because
it

brings fresh oxygen

of burning.

and removes the nitrogen and the products But a too rapid current will cool the burning- body
Thus, a flame

below the kindling temperature. " out by a gust of air.

may

be

"

blown

The lowering of the 30. The Safety Lamp. temperature below the kindling point is admirably
illustrated in the safety lamp invented by Sir Humphry Davy

to prevent explosions " -

of

"

fire-

damp
(

a mixture of marsh
in mines.

gas

292) and air

The lamp
ordinary

(Fig. 7) consists of an lantern entirely sur-

rounded by wire gauze. When it is brought into an explosive


gaseous mixture, the gases diffuse through the wire gauze, and burn
inside the lamp,

produced
the
outside

is

but the heat conducted away by


so

gauze,

that

the

gases

do not reach the ignition

temperature.

series of small

explosions inside the lamp warns the miner of his danger.


FIG.
7.

REVERSED COMBUSTION.
31. Spontaneous Combustion. oxidation the kindling temperature

25
in

Even

slow

may be reached This fact if the heat generated is not dispersed. " explains spontaneous combustions," in which oily rags, waste, etc., take fire without apparent cause. The linseed oil of paint becomes hard by absorbing
oxygen from the
air.
is

by the oxidation

Ordinarily the heat produced dissipated, but when the rags

are piled in heaps this is not possible, hence the temperature rises to the point of ignition. Coal

packed closely in poorly ventilated bunkers often


takes
fire

because of slow oxidation.

Spontaneous combustion

may

solution of phosphorus (only a small in carbon disulphide. If this solution


fire
is

be illustrated by means of a amount must be used)

is poured upon a filter on the a paper supported ring stand, phosphorus will soon take

spontaneously." The explanation of the phenomenon that the evaporation of the carbon disulphide leaves the phosphorus in the pores of the paper, where it is oxidized.

"

The heat

conducting

generated, being prevented from escaping by the nonfilter paper, soon raises the temperature of some

part of the paper to the ignition temperature of the phosphorus.

32. Reversed Combustion. bustible and the supporter of

If
its

both the comcombustion are


reversed.

gaseous,

the combustion

may

be

Thus,

oxygen
nating
reversal

may become
gas
the

the burning body and illumisupporter of combustion. This

may

be shown by a very simple experiment.

26

OXYGEN.

A bottle (Fig. 8) is supported, mouth downward, and filled with illuminating gas by disThe gas at the mouth of the placing the air. bottle is then lighted, and while it is burning
a
jet of

oxygen

is

The oxygen takes The oxygen


FIG.

fire

brought up into the bottle. at the bottle's mouth and

burns in the atmosphere of illuminating gas. jet may be replaced by a combus-

tion spoon of potassium chlorate which has been heated so that it gives off oxygen.

As the 33. Importance and Uses of Oxygen. table in 9 shows, oxygen makes up 47% of the
*

earth's solid crust

Eight ninths of

and nearly 86% of the ocean. water is oxygen ( 64), and about
of the atmosphere.

23%, by weight,
Practically
all

living

things require oxygen for

Water animals get it from the their respiration. The object of respiration air dissolved in the water.
is

to get oxygen in contact with worn-out tissues, so that they may be converted into products which the organism can readily eliminate. Among these is

The heat genthe gas carbon dioxide (cf. 281). erated in these oxidations keeps the bodies of the higher animals warm ( 25). In certain diseases the
lungs are not able to supply the body with oxygen rapidly enough from the air, so pure oxygen is used.

While plants use oxygen, and give

off

carbon

dioxide, just as animals do, yet they carry on the reverse action, i. e., use up carbon dioxide, and give

EXERCISES.
off

27

dioxide

oxygen, in building up their tissues. The carbon and water used by plants for this purpose

together contain too much oxygen, hence the excess Animals and plants are thus is given off to the air.
interdependent, the one giving off what the other As a result the quantity of oxygen in the air uses.
is

kept practically constant,


34. Exercises.

1 How many grams of mercury and of oxygen will be formed by the decomposition of 43.2 grams of mercuric oxide? 2. How many grams of manganese dioxide are needed to give, when decomposed by heat, 12 grams of oxygen? How much manganous-manganic oxide will be formed?
.

3.

duce,

Calculate the weight of potassium chlorate that will prowhen heated, 74.5 grams of potassium chloride. What
is

weight of oxygen

formed at the same time?

cubic centimeters of oxygen can be made from 4. 1.2 grams of potassium chlorate if 1 c.c of the gas weighs .0014

How many

gram?
5.

How many

posed to give 36 liters of oxygen


1.25 grams?
6.

grams of potassium chlorate must be decomwhen 1 liter of oxygen weighs


of

water?

What weight of oxygen can be obtained from 50 grams What volume will it have at C. and 760 mm.?

In light7. Name the materials used in starting a coal fire. ing a gas stove. What are the causes of the difference? 8. Name the oxides used as sources of oxygen in the order of
their stability

Where would you


9.

toward heat, beginning with the least stable one. place potassium chlorate? Devise an experiment to prove that part of the air dis-

appears in the rusting of iron.

CHAPTER

III.

MEASUREMENT OF
35. The Volumes of Gases. cult to weigh gases accurately

GASES.
Because
their
it is diffi-

quantity

is

usually given, not in weight units, but in units of volume, such as the cubic centimeter, or the liter

Hence it is important that the (cf. Appendix i). volumes of gases be determined with great accuracy.

Now, experiments with


hours, or over night.

must often stand for Meanwhile the temperature


gases

and

pressure, and, consequently, the volume, undergo

change.

Cooling will contract the volume; heating


it.

Increase of pressure will make the volume smaller; a lowering of pressure will increase

expands

late

So the chemist must be able to calcuwhat the volume of a gas, measured at any temperature and pressure, will be at any other temperature and pressure.
the volume.
36.
is

Measurement of Pressure.
in

Pressure of gases

measured

mercury.

The instrument used

atmospheres, or in millimeters of for measuring at-

mospheric pressure is the barometer (Fig. 9). The simple barometer consists of a glass tube about a

meter long, closed at the upper end, and partly


28

TEMPERATURE.
with mercury. It stands in a bath When the barometer is of mercury. made, the glass tube is entirely filled with mercury. The open end is then
filled

29

covered with the

finger,

the tube

is

inverted in the mercury bath, and the finger is removed under the mercury.

The mercury

in the tube flows out until

the level inside the tube

mm.

is about 760 in the bath. above that (30 inches)

It does

not

fall

out entirely because the

The height of it. the mercury column changes with the atmospheric pressure. Its average at sea-level
air pressure sustains

is

760

mm.

This

is

standard pressure, or a pressure of one

atmosphere.

A column of mercury 760 mm. high


tional area weighs 1,033.6 grams;

and

1 sq.
is

cm. in cross

sec-

the atmosphere upon 1 used is water, which is

iW

the pressure of If the liquid sq. cm. at sea level. as heavy as mercury, the height of
i. e.,

hence this

the barometer will be 13.6 times as great as with mercury, meters, or 34 feet.

10.4

37. Temperature. Temperature is usually measured by the mercury thermometer graduated on the The zero mark is determined Centigrade scale. by immersing the bulb in melting ice. The 100

mark

is

ard pressure.

the temperature of water boiling under standThe space on the thermometer stem

lying between these

two marks

is

divided into 100

30

MEASUREMENT OF

GASES.

and the degrees are marked off above and below the two fixed points. As mercury boils at 357 C. and freezes at 40 C. the interval between represents the range of an ordinary chemical thermometer.
COMPARISON OF ORDINARY WITH ABSOLUTE SCALE.

APPLICATION OF CHARLES' LAW.


called the Absolute Zero.

31.

Before

it

is

reached

all

liquid or solid. Instead of calling the melting point of ice 0, we may place the zero point 273 below this, that is, at Absolute Zero. The tem-

gases

become

perature scale thus produced is called the Scale of Absolute Temperature, and its readings are calle^ absolute readings. Centigrade readings may be to absolute changed readings by the algebraic addition of 273; C. thus becomes 273 Abs., -20 C. becomes 253 Abs., and 20 C. becomes 293 Abs. We have just learned that 100 c.c. of a gas at C.
1

become

100.
is

by 1^%
is

c.cXl^rV at 20 C. But multiplying the same as multiplying by ||f and this


,

the ratio of the absolute temperatures corresponding to 20 C. and C. The Law of Charles may now be stated in terms of the Absolute Temperature: Under constant pressure, the volume of a gas is
its

proportional to

absolute temperature.

1 Charles' Law 39. Application of Charles Law. enables us to calculate what volume a gas, measured

at

other

any given temperature, would occupy at any Some problems illustrate the temperature.
:

method
C.

Problem
Solution.

1.

gas measuring 80
will it

c.c.

at

C.

is

heated to 20

What volume
C.
is

have?

Let x = the volume at 20

The

absolute temperais

ture of
its

273 ; that of 20 C., 293. The gas volume will be increased. The volume at
to give the

heated, hence C. (80 c.c.)

must be multiplied by ff|

volume at 20 C.

32

MEASUREMENT OF
= 85.8

GASES.

a;

c.c.

cooled to

If 60 c.c. of oxygen, measured at 30 10 C., what will the volume become? 10 C. Solution. Let z = the volume at

Problem

2.

C., are

- 10
the

30 C. = 303 Absolute. C. = 263 Absolute.


diminished;

The gas is to be cooled, hence the volume will be new volume will be |(B of the original volume.
z = 52.08
c.c.

If Boyle's Law. 40. Volume and Pressure; the temperature of a gas is kept constant, the volume This is Boyle's Law. varies inversely as the pressure. It expresses the fact that if a gas occupies a given

volume at 760 mm. pressure it will have twice this volume at 380 mm., and half the volume at 1520

mm.
The product
volume
of

number representing the a gas and the number representing the


of

the

pressure under which the volume


therefore, a constant;
or,

is

measured

is,

vXp = constant.
Since increasing the pressure will diminish the of a gas, it will plainly increase the mass of in a Hence gas given volume, i. e., the density.

volume

Boyle's,

or,

Law,

may

sometimes called, Mariotte's be stated thus: The density of a gas a t


as
it

is

constant temperature is proportional to the pressure,

TEMPERATURE AND PRESSURE.


41. Application
of

33

Law. By using Boyle's Law we can calculate what a volume of gas, measured under a given pressure, will become under
Boyle's

any
725

other pressure.
1.

Problem
Solution.

gas measures 120


will it

c.c.

when the

pressure

is

mm. What volume

have at 760 mm.?

in question will

Since volume varies inversely as pressure, the gas be diminished in volume, for the new pressure is

the greater.

Let z = the volume at 760


c.c.)

mm. The volume


fift to give

at

725
at

mm. (120 760 mm.

must be multiplied by

the volume

2 = 114.5

c.c.

Problem

2.

of nitrogen that measures 50 c.c. at 820

What will be the volume at 650 mm., mm.?


is

of a quantity

Solution.
(x) will

Since the pressure

diminished, the

new volume

be

larger

than 50

c.c.

z = 63.08

c.c.

42. Correction for Both Temperature and PresIf we wish to determine the effect of changes sure.
in

both temperature and pressure we can make the calculation for each change separately, or we can

combine the two

in

one expression.

will its

Probkm. I have 100 c.c. of air at 20 C. and 720 mm. What volume be at C. and 800 mm.?
Solution 1

only,

and
is

the air

Let us make the correction for temperature C. and 720 mm. Then, since to be at a lower temperature, x will be less than 100 c.c.
.

(a)

let

# = the volume at

34

MEASUREMENT OF
z = 93.17

GASES.

c.c.

(b)
?/

Now,

let

us
at

make

= the volume

C. and 800

the correction for pressure, and let mm. Since the pressure is to
will

be increased from 720 to 800 mm., the volume and y will be less than x.
1/

be diminished,

= 93.17X!(MK
c.c.

y = 83.85 Solution 2.
1

It

is

better to combine the

into one operation.

Let x be the volume at

two parts of Solution C. and 800 mm.

Then

x= lOOXf H XUo. x = 83.85 c.c.

43. Correction of the Barometer Reading. Two corrections of the barometer reading are necessary for accurate work with gases:
(1)

Correction

for

Temperature.
is

height of the
to

barometer

is about 3 mm. longer this amount should hence C.; subtracted from the barometer reading at 20 " " reduced to if the volume of a gas is to be

column

the expansion of in the barometer

-The standard C. Owing mercury when warmed, the


760

mm.

at

at

20

C. than at

be
C.

C.

The

table of temperature corrections


xii.

is

given in

Appendix
(2)

Correction for Water Vapor.

When

collected

over water

it

is

saturated

a gas is with water

vapor (steam).

The

pressure exerted

by the moist

CORRECTION OF BAROMETER READING.


gas
is

35

thus

made up

of

of the

dry gas and that

two partial pressures : that of the steam. If we wish to

get the true (partial) pressure of the dry gas, we must subtract from the barometer reading the pressure The pressure of the vapor inof the water* vapor.
creases with the temperature; at 100
C., the boiling

760 mm. (cf. The table 71). of vapor pressures, reduced to millimeters of merWhen a gas is colcury, is given in Appendix v.
point of water,
it is

over mercury the partial pressure of the mercury vapor is considered o.


lected

In collecting gases over liquids the levels of liquid inside and outside are assumed to be the same ; otherwise the pressure of the gas shown by the barometer.
is

not equal to that


for the

problem

will

show how the correction


is

pressure of water vapor


Problem.
at 26

applied.
50

The volume

of a gas collected over water


is

is

c.c.

C. and 742
C.,

mm. What

the volume (x) of the dry gas

at

and under 760 mm.?

Solution.

Volume

of gas

50

c.c.

Temperature
Pressure (unconnected) Pressure of water vapor at 26
Partial pressure of dry gas Absolute temperature of 26 Absolute temperature of
Therefore,

26 C.
742

22

720

mm. mm. mm.


299

C C

273

x = 50 X IH X H&.

36

MEASUREMENT OF

GASES.

&

44. Problems Involving Standard Temperature and Pressure. The weight of a liter of a gas is

always given in the tables C. and 760 dry gas at temperature and pressure. If at any other temperature

(Appendix v) for the

mm., i. e., for standard the volume is measured and pressure (and it

usually is) the volume must be reduced to standard conditions before the weight can be calculated.
Problem 1. What is the weight of 100 over water at 20 C. and 720 mm.?
Solution.
First,
c.c.

of

oxygen measured
the dry gas at

we

find

the volume

(x) of

C. and 760
is

mm.

The

partial pressure of the water

vapor

17 mm., hence that of the dry gas is 703 mm. for reducing the volume to.standard conditions is,

The equation

Whence
The

x = 86. 18

c.c.

table shows (Appendix v) that one liter (1000 c.c.) of oxygen under standard conditions weighs 1.429 grams. The 8 1.429, or 0.1232 g. weight of 86.18 c.c. is, evidently f

f^ X

Problem
Solution.

2.

What

is

the volume, at 25

C. and 718 mm., of

5 grams of oxygen?
First get the

volume

(x) of

the oxygen at

C.

and 760 mm.


,

or 3.49

liters.

Then

calculate

what the volume

(y) will

be at 25 C. and 718

mm. from

the equation,

If

the gas

is

mm., but 718 mm.


will

collected over water, the pressure will be, not 718 23.6 mm., or 694.4 mm., and the volume
larger.

be proportionally

EXERCISES.
45. Exercises.
1.

37

What

will

be the volume at
c.c.?

C. of a gas which at 20 C.
it

has a volume of 90
C.?

At 100 C.? At 273

What volume will C.? At -250 C.?

have at

30

2. 90 c.c. of air at 20 C. became 150 c.c. when heated. What was the new temperature? 3. Under a barometer pressure of 740 mm. the volume of a gas is 70 c.c. What will the volume be under 760 mm.? 650mm.? 10 mm.? Half an atmosphere? 4. A gas measures 100 c.c. under a pressure of 400 mm. By changing the pressure the volume becomes 85 c.c. What was

the second pressure?


5.

gas measures 20
will it

liters at

10

C. and 760

mm.

What

volume

have at 30 and 720 mm.?

6. A tube containing potassium chlorate was heated, and the oxygen formed was collected over water. The volume was 450 c.c. at 40 C. and 720 mm. pressure. (a) What would the volume have been over mercury? C. (6) What would the volume of the dry gas have been at and 760 mm.?
(c)

What
If

does the oxygen weigh?


g.,

(d)

the heated tube lost 0.49

calculate

the weight

of a liter of dry
7.

How
by

water)

C. and 760 mm. oxygen at many liters of oxygen can be made (collected over heating 122.5 grams of potassium chlorate, if the
is

temperature

32 C. and the barometer height 730 mm.?

CHAPTER

IV.

HYDROGEN.
46. Occurrence. only one-sixteenth as
is

Hydrogen is a colorless heavy as oxygen. Very little

found free in the earth, but there is 'a great deal of it in the atmosphere of the sun. In the combined form it is a constituent of all living things and of most organic substances (cf. 520), such as sugar, starch, The most common petroleum, coal, and wood.

hydrogen compound

is

water.

One-ninth
is

of

it,

by weight,
in all acids
of water."

is

hydrogen.
bases.

and

Hydrogen The name means a " producer

also contained

47. Laboratory Method of Preparation. reaction between metals and dilute acids is the

The
most

convenient method of preparing hydrogen. The metals generally used are zinc and iron, and the
acids, dilute hydrochloric
Zinc

and sulphuric

acids.

+ sulphuric acid
-,

>zinc sulphate-h hydrogen.


( zinc, }
'

(
}

Composed
.

hydrogen, lph oxygen.

sulp hur>

oxygen.
zinc chloride -f- hydrogen.
(zinc, chlorine)

Zinc

+ hydrochloric

acid
38

(hydrogen, chlorine)

LABORATORY METHOD OF PREPARATION.

39

FIG.

10.

Hydrogen is usually generated in a bottle or " " " provided with a thistle," or safety tube and a delivery tube reaching to a water pan (cf. 20). The metal (zinc or iron) is placed in the bottle, and acid is added through
Apparatus.
flask (Fig. 10),

the thistle tube.


tube,

The hydrogen

escapes through the delivery

and

is

collected over water.


air, it

lighter than

may

Or, since hydrogen is much be collected by displacing air (Fig. 11).

Caution!
is

Apparatus
If

in

which
not be

being hydrogen brought near a flame!

made must

the action

between
brisk, it

may

metal and acid is not be hastened by add-

ing a few drops of copper sulphate

The copper sulphate rea acts with portion of the zinc, precipitating copper upon the zinc when copper is present as a contact
solution.
;

agent

(cf.

21), zinc acts readily

FIG.

11.

40

HYDROGEN.
acid.

upon the

The

action of zinc

and acid
(cf.

results
27).

in a very considerable evolution of heat

48. Self-Regulating Generator.


Instead of the ordinary generating a Kipp's or other self-regulating

flask,

apparatus
hydrogen.
consists of
is

may

be used to supply Kipp's apparatus (Fig. 12)


three globes.

The upper communication with the lower globe, and the middle globe with the lower globe, but the upper globe and the middle globe are not connected. The upper and lower globes contain dilute acid, but the middle globe conglobe
in

tains zinc.

This

is

the condition of the

apparatus when at rest, with the stopcock closed. When the stopcock is the opened, liquid of the upper globe
into the lower globe, and the liquid in the lower globe rises into the middle
falls

globe, thus displacing the gas of the

middle globe, and forcing

it

out through

The acid which enters the stopcock. the middle globe reacts with the zinc,
forming more hydrogen, which either escapes through the stopcock, or, if the latter is closed, forces the acid back into the lower globe and thence into the
FIG.
12.

upper globe.
globe
is

The gas in the middle thus ready for instant use.

If the metal or 49. Purification of Hydrogen. " the acid used in preparing hydrogen is of com-

PRECAUTIONS IN IGNITING HYDROGEN.


mercial
will

41

grade the hydrogen will be impure, and have a disagreeable odor. We may remove

"

of the impurities by passing the gas through a solution containing sodium hydroxide and potassium permanganate (A, Fig. 13). To remove water vapor we use a drying agent, e. g., granular calcium

most

chloride (B, Fig. 13 and

90).

FIG.

13.

50. Precautions in Igniting

Hydrogen.

Before we light a jet of hydrogen (the same precaution applies to other inflammable gases), we collect a test tube full by air
in this displacement (Fig. 11), and then carry the test tube down to a flame at least a mouth meter) case, four feet (over away. The gas in the test tube burns rapidly (" explodes ")

much air mixed with the hydrogen, but it burns the air has been displaced. We then carry the test tube (mouth down) back to the jet of hydrogen until the gas is lighted by the test tube of burning hydrogen.
if

there

is still

slowly

if

42

HYDROGEN.

51. Physical Properties.


odorless,

Hydrogen
(cf.

is colorless,

and

tasteless.

It is the lightest

substance
v).

known;

air is 14.4

times as heavy

Appendix

weighs only .09 gram, under standard conditions. When hydrogen is used as a standard
liter

One

of density for gases

(cf.

6), its relative

density

is

taken as

1.

Hydrogen
23)
c.c.
;

is less

soluble in water than

oxygen

(cf.

at 14

C.,

100

c.c. of

water

dis-

solve only 1.9

of the gas.

At the ordinary temperature hydrogen cannot be liquefied by any pressure, however great (cf. but at a low temperature and under great 197)
;

pressure the gas has been condensed to the liquid

and

solid state.

Liquid hydrogen
It

is

colorless

and
C.

iV as Solid

heavy hydrogen melts


is

as water.
at

boils

at

252.5

260

C. under 58
of

mm.
and

pressure.

Hydrogen
electricity

better

conductor
gas.

heat

than any other

52. Diffusion, or Transpiration, of

Hydrogen. -

When two
Even
if

air and hydrogen, are form a uniform mixture. brought together, they

gases,

such as

they are temporarily separated, as by a porous partition, they will pass through, and mix
completely.

But the

lighter

the

gas,

the

more
small

rapid

its

diffusion

(transpiration)
is

through

apertures.

The

rule

that the rates of transpiration


to

are inversely proportional

the square roots

of the

CHEMICAL PROPERTIES.
densities of the gases.

43

Hydrogen

diffuses four

times as rapidly as oxygen. With this explanation we can understand the following:

A porous cup (Fig. 14) is attached securely to a glass tube ending under water. If, now, a jar of hydrogen is placed over, and enclosing, the porous cup, bubbles
of gas will escape from the lower end of the tube. The increase of volume is due

to the rapid movement of hydrogen into the cup. When the jar is removed the reverse diffusion takes place. A simpler apparatus is shown in
Fig. 15. A wide glass tube has one end covered with a cap of plaster of Paris. If the tube is filled with

_^__
FIG.
15.

hydrogen, by air displacement, and the open end placed under water, water will rise in the tube.

is

53. Occlusion of Hydrogen. Hydrogen is absorbed (" occluded," or " hidden away ") in large

quantities

by

certain metals,

e. g.,

iron,

platinum,

and palladium. Under the best conditions one volume of palladium occludes 873 volumes of hydrogen. When gases are compressed, heat is liberated; hence in the enormous compression that takes place

hydrogen is set on fire. A piece platinum sponge held in a jet of dry hydrogen ignites the gas. This fact is put to use in constructing Occluded hydrogen can self-lighting gas burners. be expelled by heat.
in occlusion the of

54.
air

Chemical Properties. Hydrogen burns in In chlorine it or oxygen to produce water.

44

HYDROGEN.

It can burns to form hydrogen chloride (cf. 118). be made to unite with nitrogen to give ammonia 213), and with sulphur to give hydrogen sul(cf.

phide

(cf.

between

253). When an electric arc is produced poles of carbon in an atmosphere of hy-

drogen, the two elements unite to form acetylene


(cf.

295).

" support combustion Hydrogen does not


26)
;

"
(cf.

that

is

to say, burning wood, paper, illuminat-

ing

gas,

etc.

the

ordinary
with

combustibles

do

not continue to burn


cause
they

when placed

in hydrogen, be-

Oxygen, hydrogen. however, burns in hydrogen (cf. 32). Hydrogen is really inert at ordinary temperatures, hence an " " of hydrogen is often used in experiatmosphere ments requiring the absence of the active oxygen
of the air.

cannot

unite

55.

Union

of

Hydrogen and Oxygen.

At

ordinary temperature a mixture of hydrogen and oxygen may be kept for years without any evidence of action. The reaction

more and more rapid as the temperature is raised, until it becomes an


is

"

"

explosion

above 615 C.

Finely divided

platinum, acting catalytically (cf. 21), causes explosive union at the ordinary
temperature.
FIG.
IB.

The steam formed when hydrogen burns

UNION OF HYDROGEN AND OXYGEN.


in air

45

may be con-

densed by holding over the flame a


cold object (Fig. 16), or by allowing the products of combustion to

pass
17).

through

condenser

(Fig.

vessel of

water placed over a gas flame condenses some of


cold

the steam formed


in the

burning of

the gas.

The
flame
is

hydrogen
colorless,
FIG.
17.

but very hot. One gram of hydrogen burning in oxygen (how much oxygen is needed?) liberates 34,200 calories of heat, i. e., enough to heat 34,200 grams of water from C. to 1 C., or to heat about 340 grams from the
freezing point to the boiling point.

An

apparatus for making use


is

of this great heat evolution

the

oxyhydrogen blowpipe
FIG.
18.

(Fig. 18).

This consists of a small inner tube

communicating with a tank

of

46

HYDROGEN.

oxygen, and a larger outer tube in connection with a tank of hy-

Both gases are greatly compressed. The hydrogen is turned on and lighted; then the oxygen is allowed to escape Thus a flame is produced which is so hot that it very slowly. will melt platinum. (Platinum melts at about 1777 C.) A
drogen.
first

piece of quicklime held in the oxyhydrogen flame becomes white hot and gives off much light; this is the so-called calcium, or
lime, light.

illuminating gas

In the production of the lime light for stereopticons, The is generally used instead of hydrogen.

ordinary blast-lamp of laboratories is similar to the oxyhydrogen blowpipe, but the gases used are illuminating gas and ordinary air; as a result, the temperature produced is by no means as

high as that of the oxyhydrogen flame.

56. Reduction. Hydrogen has the power of combining not only with free oxygen, but also, in many cases, with oxygen that is in combination with other elements. Thus, if hydrogen is passed over heated copper oxide and iron oxide, it unites with the oxygen of these substances, forming water,

and

setting free copper

and iron
>

respectively.
copper
iron

Copper oxide + hydrogen Iron oxide + hydrogen

>

+ water. + water.

oxygen from a compound is and the substance that unites reduction, with the oxygen is the reducing agent. Of course
of

The removing

called

the reducing agent is oxidized (cf. 25) no reduction without a corresponding

there

is

oxidation.

Most

oxides,

24, 229,

and the nitrates, chlorates, etc. (cf. and 331), are oxidizing agents; carbon

METHODS OF PREPARING HYDROGEN.


and hydrogen are common reducing agents
275).
57.

47
(cf.

Other Methods
is

hydrogen
acids.

present in water
following are

of Preparing Hydrogen. As and in bases it may be

prepared from these substances as well as from

The

some

of the

ways

(1) By the action of the electric current upon water (cf. 61). This is called the " electrolysis of water." It takes place only when the water contains small amounts of acids, bases, or salts
(cf.

174).

The products
(cf.

of the electrolysis of water are hydro-

gen and oxygen

22).

Sulphuric acid

is

the catalyzer com-

monly

used.

(2) By the reaction between metals and water. Some metals, such as sodium, potassium, and calcium, react rapidly even with cold water, forming hydrogen and the hydroxides of the metak.

Sodium

+
(
(

water
hydrogen, |
J"
(

sodium hydroxide
>

hydrogen.

oxygen

sodium, hydrogen, oxygen

Steam

Iron Filings

FIG.

19.

Other metals, such as magnesium,


water rapidly only when
it is

zinc,

and

iron, react

with

hot, or in the form of steam (Fig.

48

HYDROGEN.

19). When steam is passed over heated metals the products are oxides of the metals, and hydrogen.

Magnesium + water
Iron -f water
)

magnesium oxide + hydrogen.


iron oxide
its

+ hydrogen.
Thus, aluminum

Compare
(3)
filings

this last reaction

with

reverse,

56.

By the action of metals upon hydroxides.


and a solution
of

sodium hydroxide give hydrogen when warmed; so does a mixture of zinc dust and powdered sodium
hydroxide
(<?/.

447).
soc^

Aluminum 4-

mm

-!

I
J

sodium aluminate+ hydrogen.


( (

hydroxide

sodium, alumi-

num, oxygen

58.

Uses

of

Hydrogen. --The uses

of

hydrogen

chiefly upon its lightness, and upon the high Because of its lightness temperature of its flame.

depend

it

may

be used to

inflate

balloons.

Its

flame

is

used in the oxyhydrogen blowpipe to melt platinum

and other high-melting metals, and to cause the incandescence of lime in the stereopticon light.
Illuminating and fuel gases consist largely of hydro296 gen, either free, or combined with carbon (cf.

and

299).

59. Exercises.
1. In what properties are hydrogen and oxygen alike? Unlike? you had 3 bottles filled with oxygen, hydrogen, and illuminating gas, respectively, how could you distinguish them? 2. What properties of hydrogen make it useful for inflating

If

balloons?

What ones make it disadvantageous?

EXERCISES.
3.

49
What

Under what conditions does hydrogen "explode"?

test

should be carried out, and how, before a jet of it is lighted? 4. Why has not the small amount of hydrogen in the air

united with oxygen?


in liters, have 1.008 g. hydrogen? 8 g. two volumes of hydrogen combine with one of oxygen, what proportions, by weight, do they unite?
5.

What volume,
If

oxygen?
in
6.

two gases whose

Calculate the relative rates of transpiration (cf. 52) of 36 and 16 are respectively. specific gravities Calculate the specific gravity of a gas which takes 4.7 times as

long as hydrogen to diffuse through a porous wall. If 7. A gas tank holding 100 liters is filled with hydrogen. trie temperature is 38 C., and the pressure 690 mm., how much

does the hydrogen weigh? How if all the hydrogen were burned?

much water would be formed

CHAPTER
WATER.

V.

60. Nature of Water. Water is so stable that it was believed to be an element until 1781. In that year Cavendish, who had discovered hydrogen in " 1766, synthesized, i.e., put together," water from and this oxygen; proved it a compound. hydrogen

61. Electrolysis
its

Water. Synthesis has for " which means a opposite, analysis, breaking
of

up," or

tearing apart," as of a compound into its or of a mixture into its ingredients. The elements, " " of water is a method electrolysis 57, 1) (cf.
of

"

decomposition,
It
is

or
car:

analysis.

ried out as follows

An
from
is

electric

current

or battery, other source (Fig, 20),

passed between plat-

inum electrodes through a 5% solution


Zn
FIG.
20.

of sulphuric acid. The electromotive force of

SYNTHESIS OF WATER.

51

the current must be over 1.47 volts. Bubbles of gas gather upon, and then rise from, the electrodes, and may be collected in tubes filled with the dilute acid and

inverted over the electrodes.


trode, or

the current enters the solution is

anode that by
;

electrode by which the positive (+) elecwhich the current leaves the

The

The solution, the negative ( ) electrode, or kathode. gas that collects at the kathode is considered electropositive, since it is attracted

by the negative charge


is

on the kathode.

The gas

at the anode

electro-

In a given time, about twice as negative. gas collects at the kathode as at the anode.
electro-positive gas
is

much The

hydrogen; the electro-negative,


(a

oxygen.
of

The

electrolysis

sodium
salt)

hydroxide

base), or of

sodium
,

sul-

phate (a

will give the

same

gases, in the
(cf.

same
183).

proportions

While catalytic agents are necessary, it is the water


itself

that

is

decomposed.

62. Synthesis of Water,

by Volume.
cisive

More

de-

than

electrolysis, as

proof of the composition of water, is the fact that


the gases hydrogen and
FIG.
21.

52

WATER.

oxygen actually unite in the proportion of two volumes of hydrogen to one of oxygen to form water.

%*

The experimental proof


(Fig. 21):

is

as

follows

is

"

eudiometer," a strong, glass tube with

two platinum wires sealed into it, near the closed end. It is filled with mercury and inverted in the bath of mercury (B). Some hydrogen is
introduced into

D~
FIG.

under mercury.

is

then

same as in A (cf. 43). A is now slipped a little more than the and oxygen is introduced, and its volume is hydrogen read as was that of the hydrogen. The
C,

22.

securely over the rubber stopper C, and the hydrogen is brought to atmospheric pressure by making the mercury level in E the

forced

off

from

A is left securely pressed over C, the leveler E is lowered so that the gases almost fill the eudiometer, and the mixture in A is ignited by an electric spark, obtained
lower end of

from a spark coil, which is passed between the platinum wires. A flash of light marks the reaction. When A is cool, the mercury
levels are

made

the same, and the excess of

oxygen
taken.

is

measured.

used up

will

The volume of oxygen be half that of the hydrogen


of

Another form
Fig. 22.

eudiometer

is

shown

in

gases are introduced into A through the opening controlled by B, and are brought to atmospheric pressure by

The

J
FIG.
it
23.

adding

mercury through C or by drawing

off at

D.

RELATION BETWEEN THE VOLUMES.

53

63. Relation between the Volumes of Hydrogen, The volumetric synthesis of Oxygen, and Steam. in as 62, does not tell us the volume water, given of the steam formed from two volumes of hydrogen and one of oxygen. This additional fact may be

learned

by the use
(Fig.
filled

of the

eudiometer must,
jacket
23)
of

apparatus of Fig. 21. The however, be surrounded by a

that

can be

with steam

^^_^^ u 2*""^
ft

or the vapor

some

^^^-^-7<cr\

"x

liquid boiling above 100

C.

The hydrogen and oxygen


in exactly the right proportions as obtained by

are

The electrolysis shown in Fig. 24. apparatus By causing the gases to comelectrolysis.
is

bine at, or above, 100 C. FIG. 24. the resulting steam does not condense. Its volume is found to be that of the hydrogen used. This experiment was performed first by Humboldt

and has been repeated many times. two volumes of hydrogen unite that proves conclusively with one volume of oxygen to produce two volumes of steam. The facts are represented graphically by the ex-

and Gay-Lussac
It

in 1805,

pression

nn
2 volumes hydrogen.

-f

nn
1

volume oxygen.

2 volumes steam.

54
64. Synthesis of

WATER.
--

The exact Water, by Weight. relation, by weight, between the hydrogen and oxygen of water is of such importance that many methods have been devised to determine it. In one method a known weight of hydrogen is
passed over cupric oxide
is
(cf.

56).

The hydrogen

The gain

and weighed. due to oxygen. is, evidently, In a second method a known weight of cupric The oxide is reduced in a stream of hydrogen.
oxidized to water, which
in weight
is

collected

water produced contains the oxygen


oxide.

lost

by the cupric

The apparatus

is

shown

in Fig. 25.

FIG.

25,

Hydrogen, purified and dried by alkaline permanganate soluand calcium chloride (C) respectively, is passed over heated copper oxide contained in a porcelain boat (D), and the water produced is collected in a U-tube of calcium chloride (E). A guard tube of calcium chloride (F) excludes the water of the
tion (A)
air.

Berzelius and

Dulong

carried out this experiment in 1819,

with the following results:

OCCURRENCE OF WATER.
Weight
of water taken

55
30.519
27.129
3.390
g.
g. g.

up by calcium
.

chloride =

Loss in weight of cupric oxide (oxygen) = Weight of hydrogen united with 27 1 29 g. oxygen =
3.39

_JL

27.129" 8.002'
the ratio of

hydrogen

to

oxygen in water.

In a third method, devised by Morley, an American, the hydrogen, oxygen, and water are all weighed. According to Morley 1 part of hydrogen combines with 7.94 parts of oxygen, or 1.008 of hydrogen with 8 of oxygen.

65.

Law

of Definite
all

Proportions by Weight.

Not only

water, but
of

compounds,
or

illustrate this

definiteness

composition:

Law

of
is

Definite

Proportions.

Thus potassium

chlorate

always

39.18% oxygen, 31.91% potassium, and 28.91% chlorine, and mercuric oxide is always 92.59% mercury and 7.41% The law is stated thus oxygen.
:

found to have the composition:

given chemical compound is always composed of the same elements united in the same proportions.

66.

Occurrence ofJWater.

As was

stated

in

9, the earth's x great body of water, the makes up about 7% of the earth's mass.

certain
places,

depth,
all

soil

which varies greatly in and rock is saturated with water.


contains a great deal (as steam)
.

The atmosphere

56

WATER.
cubic meter of air saturated with water vapor at C. contains 17 grams of it.

A
20

Water makes up a large part of all plants and The human body is 70% water. Milk animals. is 87% water, potatoes over 78%, watermelon 92%, white bread about 35%, and beef about 62%.
67. Natural

Water.

Natural

water,

whether

snow and ice, or as liquid water, is never pure. Rain water is the purest of natural waters, but in its fall takes up dust, carbon dioxide, ammonia, etc. Water that flows over, or penetrates, the earth's
as

surface

finds

many

substances to
solids

dissolve.

The

most common

soluble

in

natural water are

The gases salt, magnesium chloride, and gypsum. most commonly present are air, carbon dioxide, ammonia, and hydrogen sulphide. Water containing carbon dioxide dissolves limestone (cf. 284), hence this is usually present in natural water. Water charged with hydrogen sulphide is called sulphur water. Ocean water contains 3.5% of solids. Nearly

2.7%

is

common

salt.

68. Drinking Water. The adjective pure,'' as applied to water, means different things to dif-

"

ferent classes of people. To the chemist it means water free from all dissolved or suspended substances.

To

the

manufacturer

it

suitable for use in boilers or as a cleanser

means water on a com-

PURIFICATION OF WATER.
mercial scale.

57

To

the housekeeper

it

means water

suitable for household cleansing, for cooking, and, above all, for drinking.
Drinking water should not contain more than .03 of 1% and not more than -fg- of this should be organic. Decaying animal matter is the natural breeding place of diseaseTo be good a water should not contain producing bacteria.
solid matter,

more than traces


cation of
its

of

it.

The appearance

of a water

is

no

indi-

purity; a clear, cool, and pleasant water polluted, while an unattractive one may be harmless. " is needed " Water Analysis examination, called a

may

be

careful

to de-

termine the quality of a water. The analysis consists of a chemical examination for, the non-living ingredients, and a
bacteriological

study of the microorganisms present.

It should

an inspection of the surroundings of the source of the water, to determine whether or not kitchen drains, outbuildings, or barns may be so situated as to pollute the water.
also include

6g. Purification of

Water.

Drinking water
(2)

may
by

be purified
distillation.
(1)

(1)

by

filtration;

by

boiling;

(3)

Filtration of water conin

sists

passing
material.

it

through

The filter porous " not only strains out" insoluble substances,

but

it

assists

in oxidizing organic impurities, by bringing them into intimate

contact with

hold

filter

may
is

tube which

A housebe a porous attached to the


air.

FIG.

20.

58
faucet, or
it

WATER.

may

be a jar with a porous bottom, with

and charcoal shown in Fig. 26. an entire city is often filtered through layers of sand and gravel acres in extent and several feet deep. Tile drains at the bottom conduct the water to a reservoir. All filters should be cleaned frequently, or they themselves become
or without the gravel

The water

for

sources

of

pollution.

react used to purify with the soluble substances present, producing a 87 and 476), which carries down precipitate (cf.
finely

Aluminum salts are water by coagulation. They

often

suspended clay particles and the germs


Boiling

cling-

ing to them.
(2)

the water

kills

the microorganisms

present, and makes limestone insoluble by expelling the carbon dioxide (cf. 67 and 284). The soluble

Since the taste of fresh water due largely to the dissolved gases, boiling, like " flat." distilling, leaves the water Filtering the boiled or distilled water, or shaking it with air, restores the gases, and makes the water palatable and wholesome.

substances remain.

is

(3) Distillation

consists

in

converting

a liquid
All

and then condensing the " " than the volatile impurities more as ammonia, etc., appear in the first the distillate; all less volatile remain in
into vapor,

vapor.

water, such

portions of the still.

The
Fig.

distilling

27.

The condenser

apparatus used in laboratories is shown in is called a Liebig's condenser. It

HARDNESS OF WATER.

59

an inner tube for condensing the vapor, and an outer jacket through which cold water is kept running. Chemically puTe water is hard to prepare and keep. Even water so pure that it will leave no residue when evaporated in a
consists of

platinum dish cannot be kept pure long, for it acts upon the glass or porcelain vessels in which it is stored or used.

70.

Hardness

of

Water.

Water that contains

gypsum, limestone, magnesium chloride, etc., does " " hard not wet the skin readily, and is called water. Soap reacts with hard water, forming an " insoluble scum " (cf. 413), and thus removes the " " when it forms permahardness. Water is soft nent suds with soap. The hardness of a water may thus be denned as its soap-consuming power. Hardness

two degrees: temporary and permanent. Temporary hardness may be removed by boiling
is

of

60
(cf.

...

WATER.

" 284); permanent, only by using softeners/' such as washing powders, lime, ammonia, etc.
(cf.

435).

is

71. Physical Properties of practically odorless and

Water.
tasteless.

Pure water In small

quantities it is colorless; in large masses, blue. Water is the only substance we deal with commonly
in its three physical states of solid, liquid,

and

gas,

Ice melts at
freezes at the

C. under 760

mm.

same temperature,
ice.

if it

pressure. Water is in motion,

or if
it

it is

in contact with

If

may

remain liquid below


(cf.

kept perfectly quiet, " " C., in a superfused

condition

86).
its

begins to freeze,

the supercooled liquid C. On temperature rises to

When

freezing, water expands; 10 c.c. become 10.9 c.c. of ice. The density of water is at its maximum at

C.; its relative density is then relative density of ice is 0.92.

(cf.

6).

The

When
calories

a gram of water freezes


of heat
(cf.

it

gives off 79
is

55).

The same amount

needed to melt a gram of ice; the heat of solidification of water is equal to the heat of fusion of ice. Water, even ice, evaporates at all temperatures. The vapor tension of each at C. is 4.5 mm. At 100 C. the vapor tension of both water and steam is 760 mm.; at 150 C. it is 3,581 mm. The boiling point of a liquid is the temperature at which the
pressure of
its

vapor equals that of the atmosphere

CHEMICAL PROPERTIES.
in contact with
is

61

it;

hence the boiling point of water

100

C. under 760
is

mm.

pressure.

Steam
gen.
c.c.

One

a colorless gas, 9 times as heavy as hydrocubic centimeter of water gives about 1200

of steam.

To

convert

1 g. of

water at 100

C.

C. requires 537 calories. This The heat of is the heat of vaporization of water. condensation of steam just equals it.
into
specific heat of water (1) is high; more heat needed to warm a given weight of water 1 C. than is needed for the same weight of any other
is

steam at 100

The

substance except hydrogen (see Appendix iii) Water is a poor conductor of heat and of the electric current
.

(c/.174).

The chemical proper72. Chemical Properties. ties of water are given in detail in other sections.
They
(1)
it is

--

are

Water is very stable ( 60, 73, and 311), but decomposed by the electric current. (2) It reacts with some metals to give basic 57 and hydroxides (or oxides) and hydrogen (cf.
74).
(3)

It

reacts

with

certain

non-metals,

such as

chlorine
(cf.

(4)

bases,
(cf.

and fluorine, to give acids and oxygen 119 and 317). Water unites with oxides of metals to give and with oxides of non-metals to give acids 161 and 162).

62
(5)

WATER.

Water
(cf.

unites with
88,

many compounds

to

form

hydrates

"water

of crystallization").

73. Dissociation of

Water by Heat.

Above 1000 C. steam undergoes a slight decomposition into hydrogen and oxygen. The amount increases as the temperature No matter how long steam rises, but at 2000 C. is only 1.8%. is kept at 2000 C., the amount of the decomposition cannot be made greater, because the elements recombine as rapidly as they are separated. A decomposition like that of steam, in which there is equilibrium between decomposition and combination, is called a dissociation. Above 2000 C., the dissociation will be greater than 1.8%, but there will be equilibrium, as at 2000 C. If the temperature is lowered, enough hydrogen and oxygen recombine to produce equilibrium at the lower temperature.

Metals upon Water. We com" " to substances like metal These are all fairly iron, copper, silver, gold, etc. and ductile 8). hard, heavy, malleable, (cf. They melt at a high temperature, and do not react rapidly with air or water, under ordinary conditions. The metals named in 57 (2) differ from the common
74. Action
of

monly apply the name

metals in

(cf. 408, Table), soft (except calcium, which has the hardness of lead), and act so rapidly with ordinary air that they must be kept under kerosene or ligroin. They

many

respects.

They

are light

have a metallic

luster

tarnishes quickly. giving hydrogen and the hydroxide of the metal.


The action of sodium
is typical.

when freshly cut, but this They react rapidly with water,
When
a piece of
it is

thrown

WEIGHT RELATIONS.
upon water

63

(this is done at arm's length, and a piece of glass is held between the face and the dish to avoid danger from spattering), the heat of the reaction melts the sodium, and the globule

of metal swims about until used up. A lighted match brought near the sodium sets the escaping hydrogen on fire. The hydrogen may be collected by placing the sodium in a short piece (1 cm.) of glass tubing, and then plunging it quickly, by the use of tongs, under the in a water-pan.

mouth of an

inverted bottle of water standing

The

dilute solution of

feels soapy,

ration of
solid
(cf.

sodium hydroxide formed by the reaction and turns red litmus blue. Evapothe water would leave the sodium hydroxide as a white
has a
bitter taste,

412).
is

When potassium
the

put upon water, the heat of reaction

sets

hydrogen on fire.

Calcium reacts with water more slowly than sodium, but gives
corresponding products.

75-

Weight Relations
a

If

known weight

of

of the Reaction ; Hydroxides. sodium is added to water,


is

and the hydrogen formed

collected, the relation

by

weight between the hydrogen and the sodium that displaced it can be readily determined. Experiment shows that it takes 23 grams of sodium to set free 1 gram of hydrogen. If 23 grams of sodium were actually added to water, and the excess of water were evaporated, the sodium hydroxide would weigh 40 grams. // no new matter is produced by the reaction, then the production of 40 g. of sodium hydroxide and 1 g. of hydrogen must require 18 grams of water in addition to the 23 grams of sodium:

23+18 = 40+1.

64
Experiment shows
Sodium + water
23
g.

WATER.
this is actually the case
>
:

sodium hydroxide + hydrogen.


40
g.

18

g.

Ig.

Or we may write
<

it

thus: (
-I

bodium-h
23
-j

g.

hydrogen, hydrogen, 1 g. oxygen, 16 g.

1 g. )

>
)

sodium, 23 g. hydrogen,! g. oxygen, 16 g.

)
>

-{-hydrogen.
.

1 g.

For potassium and water the weight relations are: Potas(


<

sium-h 39 g.

hydrogen, 1 g. hydrogen, 1 g. oxygen, 16 g.

)
>

f
-j

potassium, 39 g. ) hydrogen, 1 g. f ) oxygen, 16 g.

+ hydrogen.
1 g.

It is plain that in both cases the hydroxide contains half the hydrogen of the water used, the other half

being set free. We may thus define a hydroxide as water with half of its hydrogen replaced by a metal.

By

proper methods sodium

may

be

made

to react with sodium


1

hydroxide; 23 grams of sodium again liberate gen; this time from the sodium hydroxide,

gram

of hydro-

Sodium hydroxide-}- sodium


40
g.

23

g.

sodium oxide + hydrogen. 62 g. Ig.


of

That the reaction is a replacement more evident if we give details


:

hydrogen by sodium

is

Sodium, 23 g. Hydrogen, 1 g. Oxygen, 16 g.

)
>

-(-sodium 23 g.

1
(

sodium, 23 sodium, 23 oxygen, 16

g. ) g. > g. )

-hhydrogen.
1 g.

In 64 and 65 we 76. Equivalent Weights. learned that the Law of Definite Proportions applies
to combination of elements;

75 shows that

it

applies

EQUIVALENT WEIGHTS.

65

also to the replacement of one element by another. Chemists use two sets of numbers to represent

equivalent amounts of the elements, that is, to represent the proportions by weight in which the elements combine with, or replace, one another.

One
will

of these sets

is

called the equivalent weights ;

the other, the atomic weights. be studied later ( 152).

The atomic weights They depend upon

the equivalent weights, but are not identical with

them. The equivalent weight of an element is the weight of it, in grams, that combines with, or replaces, 8

grams of oxygen or

gram (more

of hydrogen. equivalent to each other, for they represent the proportions in which the two elements unite to form

The weights taken

exactly, 1.008 g.) as standards are

water.
The
easily

following table gives


:

some

of these weight relations in an

scanned form

66

WATER.
we
treat a

get the equivalent weight of zinc,


zinc with

known weight

of

some

acid, collect

and get the weight

of the hydrogen,

and

of hydrogen.

calculate the weight of zinc needed to produce 1.008 g. Or we may convert the zinc into zinc oxide, and

calculate

how much

zinc

would have united with 8

g. of

oxygen.

77. Exercises
1.

and Problems.

If 10 c.c. of
is

the mixture

hydrogen are mixed with 10 c.c. of oxygen, and exploded in a eudiometer, which gas is left? How

much of it? How much steam is formed?


2.

When

1.89 g. water were formed,

hydrogen was passed over some heated cupric oxide and the cupric oxide lost 1.678 g.
of

Calculate

the weight

oxygen combined with

gram

of

hydrogen. 3. In an experiment, 13.98 g. iron were dissolved in dilute sulphuric acid, and the hydrogen formed measured 5.6 liters

under standard conditions.


iron?

What

is

the equivalent weight of

of potassium is 39. How many hydrogen are formed when 5 grams of it act upon water? How many grams of water are used up? How much potassium hydroxide is formed? 1.336 g. calcium reacted with water, 808 c.c. 5. When hydrogen were collected over water at 15 C. and 753 mm.
4.

The equivalent weight


of

grams

Calculate the equivalent weight of calcium. 6. How would you determine the per cent of water in a

potato?
divisible

evidence is there that the hydrogen of water is more than the oxygen? 8. For what units of measurement is water taken as a standard?
7.

What

CHAPTER

VI.

SOLUTION AND CRYSTALLIZATION.


78.

Nature

of

Solution.

By

solution,

or

dis-

solving, we generally mean the uniform mixing of a solid or gas with some liquid, called the solvent.

The

The resulting mixture is called a solution. dissolved substance is called the solute. Water,

The alcohol, and ether are common solvents. solute imparts some of its properties, such as taste
and
color, to the solution,

but

its particles

cannot

be seen, and they


stands.

will

not settle

when

the solution

or not.

All true solutions are clear, whether colored Particles that settle out on standing are

said to be suspended in the liquid.

they make the liquid turbid. can usually be filtered out;


cannot.

While suspended Suspended materials


dissolved substances

The volume

of a solution

the solvent alone, solvent and solute together.


of

greater than that of but usually less than that of


is

considerable

amount

powdered sugar may be added to a vessel apparently full of water without causing an overflow, while a much smaller quantity of an insoluble substance, such as sand, cannot.
79. Solubility.

By

the solubility of a solute


67

we

68

SOLUTION AND CRYSTALLIZATION.


the

mean

maximum amount

of

it

that can be taken

up by a given quantity of solvent, in the presence of an excess of the solute. In the case of solids, solubility is expressed in the number of grams of solute for each 100 grams of solvent, at some definite temperature. Of course, any amount less than this

maximum

can be dissolved.

When no

solvent

is

named, water is understood. By the concentration of a solution

we mean

the

weight of solute actually present in a given quantity of solvent. A solution having a small concentration of solute is said to be dilute one having a large concentration is said to be concentrated one at maxi; ;

mum

concentration, in the presence of an excess of the solute, is saturated.


GRAMS SOLUBLE
SUBSTANCE.
IN 100

GRAMS WATER.

CONDITIONS THAT AFFECT SOLUBILITY.


(1) (2)
(3)

69

.Character of the solute itself. Character of the solvent.

The

temperature

at

which

solubility

is

de-

termined.
150

140

130

'

)C. 10

,20

30

40

50

60

70

80

90

100

FIG

28.

Temperature SOLUBILITY CURVES.

(1) The influence of the nature of the solute is shown clearly by " Soluthe table, 79, by Appendices vii and viii, and by the

Curves (Fig. 28). A substance parison with other substances. There


bility

"

is
is

insoluble only

by com-

probably no substance Both strontium sulphate and barium without some solubility. " sulphate are called insoluble," but while the former requires

70

SOLUTION AND CRYSTALLIZATION.


its

8,000 times

own weight

of

water to dissolve

it,

the latter

solid requiring less than 100 times its requires 400,000 times. of solvent for solution is considered readily soluble; one weight

needing between 100 and 1,000 times its weight, difficultly soluble; one needing more than 1,000 times its weight of solvent is called
insoluble.
(2)

The

solubility of a substance in one solvent has

no relation
very solu-

to

its solubility in

another.

Thus, sugar and

salt are

ble in water

but insoluble

in ether.

Water

is

the most

common

solvent for inorganic substances; alcohol is next. In pharmacy, an alcoholic solution is called a tincture. Alcohol and ether
are the
(3)

most common solvents

for organic

compounds.

Temperature as a solubility factor is shown in the table The rapid increase of and in the Solubility Curves (Fig. 28) with rise is usual with solids. Some, of solubility temperature
.

however, like
as at

salt,

have almost the same

solubility at 100

C.,

Others, like calcium hydroxide are less soluble in hot than in cold water.

C.

and calcium sulphate,

81. Properties of Solutions.


boil at a higher

Solutions of solids

temperature and freeze at a lower

temperature than the pure solvent.

Thus a saturated
at 760

solution of salt in water boils at about 109

21 C. The rise of the boiling mm., and freezes at point and the lowering of the freezing point are
smaller,
of course, for less concentrated solutions.

The

specific gravity of solutions of solids is greater

than that of the solvent.


specific gravity of 1.026.

Thus, sea water has a

82. Solubility of Liquids. Liquids dissolve in other liquids, but we usually speak of the solution as a mixing of the liquids. Water and alcohol are

SOLUBILITY OF GASES.

71

miscible in all proportions, but ether and water are immiscible. Of course the term " immiscible," " " like insoluble (cf. 80), must not be taken
It means simply that the solubility of literally. water in ether and of ether in water are small. After equal volumes have been shaken together,

they separate again into two layers, the lighter, Chloroform and ether, on top (cf. Appendix v). water are also immiscible, but here water forms the

upper

layer.

Gases dissolve in liq83. Solubility of Gases. as solids and other uids, just liquids do, up to the of The saturation. factors of solubility are point
the same as for solids and liquids, with the addition
of pressure.
Difference of Solvent.

of water dissolve 2.1 c.c. hydrogen, while the


alcohol,
Effect

Under standard conditions 100 c.c. same volume of

under the same conditions, dissolves 7 c.c. hydrogen. Gases show a decrease of solubility of Temperature.

as the temperature rises. of oxygen at C., 2.9

Thus 100
c.c.

c.c.

of water dissolve 4.1


c.c.

c.c.

100.
gases.

50, and none at At the boiling point water usually gives up all dissolved
at 15, 1.84
at

This

is

Solubility of Different Gases.


classes according as
(1)

not true of hydrogen chloride (cf. 127). Gases may be divided into two

they are,

Very

soluble, or (2) moderately soluble.

To

the very soluble

gases belong ammonia, hydrogen chloride, sulphur dioxide, etc.

One
of

c.c.

of water,

ammonia, 505

c.c. of

under standard conditions, dissolves 1146 c.c. hydrogen chloride, and 80 c.c. of sulphur
is

dioxide.

Solution, in such cases,

partly union with water.

72
Thus the
(cf.

SOLUTION AND CRYSTALLIZATION.


solution of

ammonia

contains

ammonium

hydroxide
(cf.

209),

and that

of sulphur dioxide, sulphurous acid

259).

To the moderately soluble gases belong oxygen, hydrogen, and nitrogen, of which 100 c.c. of water, under standard conditions, dissolve 4.1 c.c., 2.1 c.c., and 2 c.c. respectively.
Effect of Pressure

upon

Solubility.

The

solubility of a gas in

a given solvent, at constant temperature, is proportional to the pressure. This is Henry's Law. It applies to moderately soluble
gases, not to such gases as

ammonia,

etc.

Under standard conIf

ditions 180 c.c. of carbon dioxide dissolve in 100 c.c. water.

100

c.c.

of

water are saturated with the gas at

C.,

under half

an atmosphere pressure (380 mm.), and the gas is expelled and collected at C. and 760 mm., its volume will be 90 c.c. Under two atmospheres, at C., 360 c.c. of carbon dioxide dissolve.

and Supersaturated There are two methods in common use


84. Saturated

Solutions.

for saturating

a solution, at the ordinary temperature, with a In the first, the solution is shaken or stirred solid. with an excess of the solid until saturation is reached In the second method the solution is (cf. 79). heated with enough solid to produce saturation at a higher temperature, and the solution
to the ordinary temperature.
is

then cooled

The

excess of the

solute usually crystallizes out. If, however, none of the solid solute remained in

contact with the solution, some solutes will not crystallize out on cooling, even though present in
larger
tion.

amount than necessary

to saturate the solu-

Such solutions are said to be supersaturated. Sodium chlorate, and sulphate, thiosulphate

CRYSTALLIZATION.
("

73

crystal of the solute causes them to become saturated, the excess of solute being deposited. Jarring the solution, or introduction of dust particles, may cause a crystal of the solute to be formed (cf. 71).

hypo

")

form supersaturated solutions.

85.

Energy Changes during Solution; Freezing

a gas dissolves in a liquid, heat is generally liberated, but when a solid dissolves, heat is usually absorbed. Thus, when equal parts, by weight, of water and ammonium nitrate are

Mixtures.

When

mixed at

Some

C. the temperature falls to 15 exceptions to the rule are given in 88.

C.

The energy that disappears when solids dissolve is used in changing them to the dissolved state. Salt and ice form our most common "freezing mixture." The temperature can be brought down to the freezing point of saturated brine ( 21 C.). In the
mixture the temperature falls because heat is absorbed both in the dissolving of the salt and in the melting of the ice. The hydrate of calcium chloride (cf. 433) and ice give a mixture
ice-salt

freezing at about

40 C.

from solution
crystallize

86. Crystallization. Solids generally separate in regular masses, called crystals. To

a solid from solution, we commonly use


of
84,
i. e.,

method

2,

we

let

the hot, saturated

Crystals may also be formed by slow of the solvent. The more slowly crystalevaporation
solution cool.
lization takes place,
crystals.

the larger

and more

perfect the

Sometimes

crystals are allowed to

form

74

SOLUTION AND CRYSTALLIZATION.


string suspended in the solution, as in the "

upon a
case of

rock-candy/'

also

Crystals are formed, not only from solution, but " by the freezing of a liquid. This is crystalfusion.'
7

from and melted


lization

Thus, water, melted sulphur,


solidify

zinc, all

in

crystalline

form.

When

liquid water freezes, the ice crystals fit closely 194) together, but when atmospheric water (cf. solidifies, in snow and frost, the crystal-masses are A description of crystal forms is given separate.
in

Appendix

xi.

" " Just as some solutions remain supersaturated when cooled, " so some liquids remain superfused," that is, they do not solidify at the temperature at which the solid form melts. Crystallization
is

effected, as in the case of a supersaturated solution,

with a crystal of the solid. When a superfused liquid becomes solid, the temperature rises to the true

by

"

inoculation

"

melting point.

When a 87. Precipitation and Effervescence. hot, saturated solution is cooled suddenly, the solid that separates out will consist of very small crystals
be amorphous, i. e., it is called a precipinon-crystalline. tate. Precipitation is also brought about (1) by adding to a solution a solvent in which the solute is insoluble; or (2) by a chemical reaction in which a new, insoluble substance is formed. When gases separate rapidly from solution, the " effervesce." solution is said to Thus, a mixture
(" crystal-meal "),

or

it

will

In either case

WATER OF CRYSTALLIZATION.

75

of zinc and dilute sulphuric acid, evolving hydrogen, and " soda water/' from which carbon dioxide is

escaping, both effervesce.


88.

Water

of Crystallization, or of Hydration.

By water of crystallization we mean the water with which some substances combine when they are crysA substance containing water tallized from water.
of crystallization is called a hydrate. The hydrate deprived of its crystal water gives the anhydrous

The loss of crystal water by a hydrate accompanied by a loss of crystalline structure and by other changes in properties. Thus blue vitriol,
substance.
is

a hydrate of cupric sulphate,


solid

is

which

loses

water when heated.

a blue, crystalline A white

powder, anhydrous cupric sulphate, remains. The anhydrous substance has its own crystalline form. It cannot be crystallized from water, because the product is then the hydrate, blue vitriol. However, it dissolves in concentrated, hot sulphuric acid, and By crystallizes out, on cooling, in white needles.

no means

all crystalline

substances contain crystal


etc., crystallize

water; cane sugar, salt, as anhydrous substances.

from water

The union
(1) (2) (3)

of

water with an anhydrous substance

is

a chemical

reaction, because,

A new substance is formed;


There
is

an energy-change; generally heat

is

evolved;
(cf.

The substances combine


108).

in definite proportions

10,

65,

and

76

SOLUTION AND CRYSTALLIZATION.


solids cause the

While most

temperature to

fall

when they

(cf. 85), some anhydrous substances, such as anhydrous cupric sulphate, sodium carbonate, and calcium This is due to the chloride, dissolve with rise of temperature. fact that they combine with some of the water. When the

dissolve in water

hydrates of these substances dissolve, heat is absorbed. Water is often enclosed between Decrepitation.

crystals,

and escapes

explosively (as steam)

when they

are heated.

This

Examples of subproduces "crackling" or decrepitation. stances that decrepitate when heated are common salt and
potassium sulphate.

and Deliquescence. When a water on to the air exposure hydrate " it is said to effloresce. Such a substance is washingSome ansoda," a hydrate of sodium carbonate. hydrous substances take up water from the air and
89. Efflorescence
loses its crystal

form hydrates. If so much water is absorbed that the hydrate becomes moist, or dissolves, the subis said to deliquesce. Anhydrous calcium substance that chloride illustrates deliquescence. absorbs moisture from the air is said to be hygro-

stance

scopic.

The crystal water of a hydrate escapes when its vapor pressure exceeds that of the water vapor of the air; in the case of a deliquescent substance, however, the water vapor of the air has the greater pressure. Blue vitriol holds its water of crystallization under ordinary conditions, but effloresces in dry air.

Substances used to remove 90. Drying Agents. water vapor from gases, or dissolved water from liquids, are called drying, or dehydrating, agents. Thus

EXERCISES.

77

calcium chloride was used to dry hydrogen (cf. 49). It may also be used to remove dissolved water from
ether. Similarly, anhydrous cupric sulphate remove water from alcohol.
will

(cf. 431) is a dehydrating agent because it combines readily with water to give slaked lime calcium hydroxide.

Quicklime,

i. e.,

calcium oxide

91. Exercises.
1.

Would an underground water in contact with carbon


if it

dioxide

dissolve more, or less, of the gas than

Why? What would


surface?
2.

occur

if

were at the surface? such a water were brought to the


e.

Why
etc.,

is

it

that insoluble substances,

"
g.,

sand,

burnt

alum,"
3.

have no taste?
salt,

How

could you separate a mixture of

white sand, and

iron filings so as to recover each?

Suggest a method of separating a mixture of potassium and sodium chloride so as to recover almost all of the " nitrate. See 80. Solubility Curves," " " 5. Why does dry salt snap out of a dish when heated?
4.

nitrate

6.

Calculate the per cent of potassium dichromate in a solu-

tion containing 15 g. of dichromate and 120 g. water. 7. When 20.4 g. of a saturated solution of a solid were

evaporated to dryness, 5.4


its solubility.

g. of

the solid remained.

Calculate

8.

When

14.3 g. of

crystal water

were

lost.

a certain hydrate were heated, 9 g. of Calculate the per cent of loss. Cal-

culate the

volume

of the

steam formed at 150 C. and 720

mm.

CHAPTER

VII.

FUNDAMENTAL LAWS AND THEORIES.


of Reactions. --The fundamental 92. Classes fact regarding every chemical change is that at least

formed ( 3). If the new substance is an element, it can have been formed only by the decomposition of a compound if a compound, only by the decomposition of a more complex compound, or by the union of certain elements. Matter
one new substance
is
;

not created or destroyed in a chemical change, but there is simply a rearrangement of elements. This is apparent when we classify chemical reactions.
is

There are four

classes

1. Decomposition. Elements in combination become separated by a change of conditions, as when mercuric oxide is decomposed by heat into mercury and oxygen. Such reactions

may
in

be represented by the general expression,

AB

A-f B,

which AB is the compound, and which it is broken up.

and

are the parts into

2. Combination. Elements (or compounds) existing apart unite to form a (or another) compound. Thus, hydrogen and oxygen unite to form water. The general expression is

A+B
3.

AB.

Replacement. replacement reactions an element takes the place of one of the elements of a compound,
In the
78

common

LAW OF MULTIPLE

PROPORTIONS.

79

and the replaced element is set free. Thus, zinc and dilute sulphuric acid give zinc sulphate and hydrogen ( 47). The general
expression
is

A+BC
4.

AC+B.
In this kind of reaction we have

Double Decomposition.
all
is

a concurrence of
pression

the other three kinds.


>

The

general ex-

AB+CD
To permit such an exchange
and

AD+BC.

of elements to take place,

AB

be decomposed, and then recombination of their elements must take place in a new way. The final result is that A has replaced C, and D has replaced B. An excellent illustration of double decomposition is the reaction of mercuric chloride with potassium iodide (cf. When 4).
first

CD

must

the

these substances are triturated, i.e., ground together, in a mortar, products are mercuric iodide and potassium chloride.
illustration
is

Another
chloride

the reaction between solutions of lead


iodide.

and potassium

The products

are lead iodide,

which appears as a yellow precipitate, and potassium chloride, which remains in solution.
93. Conservation
of

Matter.

Since

chemical

changes "are only rearrangements of elements, we understand why the sum of the weights of the substances that react is always equal to the

sum

of the

weights of the products.


of the

This

is

the chemical form

law of " conservation of matter." It has proved true in every case that has been examined.

The Law of 94. Law of Multiple Proportions. Definite Proportions ( states that 65) any given compound always contains the same elements united
in the

same proportion.

further fact

must now be

80

FUNDAMENTAL LAWS.

considered, viz., that the same two (or more) elements may unite in different proportions to form different

compounds.
Thus, hydrogen and oxygen form two distinct compounds,
water and hydrogen peroxide (cf. 339) carbon and oxygen form carbon monoxide ( 286) and carbon dioxide ( 276) carbon and
;
;

hydrogen form marsh gas


proportions,

291), ethylene,

and

acetylene.

The

by weight,
:

of the constituents of each are given in

the following table

Water.

> >
>

Hydrogen peroxide. Carbon monoxide. Carbon dioxide. Marsh gas.

>
)

Ratio of hydrogen to oxygen, Ratio of carbon to oxygen,


Ratio of carbon
to hydrogen,

(
(

1 1

16.
4.

j
{

3 3
j?

J
:

All of the cases

named

illustrate the

ple Proportions, which // two elements form

may

Law of Multibe stated as follows -

compounds with each one element which comthe other, different weights of bine with a fixed weight of the other bear a simple ratio to one another.
several

The law

John Dal ton,

of multiple proportions was stated in 1804, from the consideration

by
of

by

only a few compounds; but it has been confirmed the work of the past century, and is one of the

fundamental principles of Chemistry.

The Atomic Theory and the Law of Definite - - To explain the laws of definite and Proportions.
95.

multiple proportions; Dalton devised the hypothesis

LAW OF MULTIPLE
that matter
particles,
is

PROPORTIONS.

81

composed of atoms, or indivisible that the atoms have weight, and that

All the

chemical combination consists in the union of atoms. atoms of any one element, he assumed, have
of different elements will

the same weight; atoms have different weights.

Suppose one atom of one element (let us call it A) unites with one atom of another element (B), and so on throughout the whole

mass of the two elements; it is evident that if there is the same number of atoms of each kind, none of either kind will remain uncombined when the action is complete. Let us suppose, further, that the atoms of B are twice as heavy as the atoms of A. Then, if the elements unite atom for
atom, the resulting compound

ments
parts,

will necessarily contain the elein the proportion of one part, by weight, of to two

by

weight, of B.

Or,
of

if

we analyze the compound confor atom,

sisting of

and

united

atom

and

find that

it

con-

tains one part,

by weight,
is

A to two parts of B, we must conclude


atom
of A.

that the

atom of B

twice as heavy as the

In the light of the atomic theory, therefore, chemical action must take place between definite

The theory is thus an exweights of substances. of of the law definite planation 65). proportions (cf.
96. Explanation of the
tions.

Law
is

of Multiple Propor-

--The atomic

theory

the explanation not

only of the law of definite proportions, but also of that of multiple proportions. For, if atoms are elements combine with one another that indivisible, in more than one proportiorirmust do so in some way
that will not require the dividing of an atom; that

82
is

FUNDAMENTAL LAWS.
to say, the elements

and

B must

unite in the

proportion of one atom of A to one of B, or one of A to two of B, or one of A to three of B, or two of A


to three of B, etc.

atom of B is twice as B and combine atom for atom, A; it is evident that the compound formed will contain the elements in the proportion of one part, by weight, of A to two parts of B but if one atom of A unites with two atoms of B, the resulting
Let us suppose, as in
of
95, that the

heavy as that

then,

if

part,

compound will contain the elements in the proportion by weight, of A to four parts of B.

of one

Thus,
follows

if

we assume
elements

the

atomic hypothesis,

it

that

another in

which combine with one more than one proportion must do so

according to the law of multiple proportions.

- - The atomic Weights. hypothesis the laws of definite and multiple proexplains portions by the assumption that the atoms have definite weights. We have no means of finding their, actual weights, but we can get some ideas regarding their relative weights. These are called the atomic learned in As we weights. 76, the atomic weights are closely related to the equivalent weights. In some cases, as with sodium, potassium, chlorine, etc., the two weights have the same numerical value, but in other cases the equivalent weight must be multiplied by some integer to give the atomic weight. Thus, the equivalent weight of calcium is 20; its atomic weight, 40. But while the equivalent weight
97.

Atomic
"

"

ATOMS AND MOLECULES.

83

can be determined without any assumption, except that of a standard, the atomic weight of an element can be selected only by the use of certain theories. The description of the methods of obtaining atomic weights is given in Chapter XIII. We may, however,
use the atomic weights at once. They represent the proportions, by weight, in which the elements

but they represent a great deal more; hence, they are used
unite, just as the equivalent weights do,

in place of the equivalent weights. The following list contains the approximate atomic

weights of some important elements.


list is

The complete

given in Appendix

iii.

84

FUNDAMENTAL LAWS.
composed of other particles, Only by some such assumption
is

assume that matter


called molecules.

can they explain


ties of gases as

Charles
lecular

(cf.

(for the present, at least) the properexpressed in the laws of Boyle and 38 and 40). We reconcile the mo-

hypothesis with

the

atomic hypothesis by

assuming that the molecules are usually more complex than the atoms; that they are, in fact, composed of atoms. Atoms are thus thought of as the smallest possible particles of the elements (see, however, 441) that can take part in a chemical reaction, while
the molecule
is

the physical unit of matter,

i. e.,

it is

the smallest portion of any substance, simple or compound, that can exist by itself.

To
we

illustrate:

The

mined by the properties


cule.

physical properties of water are deterof the water molecules; it is only when

subject water to a chemical change that we divide the moleThen it is that the properties of the oxygen and hydrogen atoms come into play.

The molecules of elements consist of atoms of only one kind; while the molecules of compound substances contain atoms of two or more kinds.
Properties of Molecules.
:

99.

Molecules are very small

Lord Kelvin estimates that

1 c.c.

of a gas, under standard conditions, contains not less than 100 million million million of them (100,000,000,000,000,000,000). The distances between the molecules of gases are about 1,000

times as great as the diameters of the molecules. When gases are compressed, it is the distance between molecules that is

made

smaller, not

the molecules

themselves.

By

"

distance

THE MOLECULAR THEORY.


"

85

we mean average distances, for molecules between molecules are not at rest, but in motion. Mokcular motion is heat. The rapidity of the motion determines the temperature. The cause of the motion is the inherent energy of the molecules. The direction of the motion is along straight lines, except as the molecules collide with one another, or with the walls of the con" " much as a person occupy space taining vessel. Molecules " " a room, not by filling it completely, but by moving occupies

about in

it.

100.

The Molecular Theory and Physical


of

State.

The theory

molecules explains the differences

between the gaseous, liquid, and solid states. The energy of the particles of a gas is so great that the " " fills any space presented to it, and exerts gas
pressure upon the walls of a containing vessel. The attraction between molecules (cohesion) is slight in

Because of molecular motion, gases do not remain in layers according to their densities, but mix in all proportions, giving a mixture of uniform 200). composition. The air is such a mixture (cf.
gases.
In the case of liquids, the cohesion between molecules is greater than with gases, yet the molecules move about freely enough to permit the liquid to take the form of the containing vessel.

Because the molecular energy is less, diffusion is more slow than with gases, and the extent to which it can take place is often limited. Thus, ether dissolves in water, and water in ether,
to a certain limit (cf. 82) In solids, cohesion predominates, and the molecules do not usually alter their relative positions. As a result, a solid has a

up

definite

form.

Molecular motion has not ceased, very slowly.

however,

although

solids diffuse into other solids

case of

86
"
solid diffusion

FUNDAMENTAL LAWS.
"

was the formation

of the alloy, solder

(cf.

512 and 515), from its constituents without melting. The metals were subjected to a pressure of about 6,000 atmospheres, in steel molds, and diffused into each other, as gases do at ordinary pressure. The solder had the same properties as that made by
melting the constituents together.

101. Exercises.
1.

effloresce, conservation,

Give the origin and meaning of triturate, deliquesce, marsh gas, atom, molecule, hypothesis,

theory, cohesion, adhesion. 2. In which of the cases given in this chapter does an element

have more than one equivalent weight?


theory accounts for the effects of temperature and How does this theory pressure upon the volumes of gases? explain the evaporation of liquids? The dissolving of solids?
3.

What

the basis of this theory, must crystals be allowed to form slowly if they are to be large and perfect (cf. 86)? Why do solids generally dissolve more readily in hot water than in cold, while gases do not? 4. Look up, in the Appendix, the atomic weights of sodium,

Why, on

potassium, chlorine, oxygen, hydrogen, carbon. figures somewhat different in the two columns?

Why

are the

^
bols

CHAPTER

VIII.

EQUATIONS AND NOMENCLATURE.


102. Symbols, Formulas, and Equations. place of the names of substances chemists use

In

sym-

and formulas. capital and a small

symbol is a capital letter, or a letter, that stands for an element.


letter

The

letter

used

is

the initial

of the

name

of the

When two names begin with the same letter a second letter is added to distinguish them. Thus the symbols C, Cl, and Ca stand for carbon, chlorine, and calcium respectively. Some symbols are derived
element.

from the Latin or Greek, e. g., Hg for mercury. A compound is represented by the symbols of

its

elements written side by side. The resulting exfor mercuric is a formula. Thus stands pression HgO
oxide,

and HC1

for hydrogen chloride.

An
of the

equation stands for a reaction. It is made up symbols and formulas of the factors and the
(cf.

products

5).

Thus, the equation for the reaction between sodium and water

Na+H
Na is the symbol of
water
is

NaOH+H.
;

sodium (from natrium)

H, that

of hydro-

gen; 0, that of oxygen.

The formula

H 0, for water, shows


2

that

composed
for

NaOH,

and oxygen; while the formula sodium hydroxide, shows that sodium hydroxide is
of hydrogen
87

88

EQUATIONS AND NOMENCLATURE.

a compound of sodium, oxygen, and hydrogen. The sign " " " is read is read and." give," or produce," and the sign The equation is read in the direction of the arrow. Two arrows

are generally used in an equation showing replacement or double decomposition (cf. 92); one to show the direction in which the equation is to be read, and the other, what becomes of the

products.

The equation given above thus becomes,

Na+H

>

NaOH+H T

The arrow pointing upward

indicates a gas;

one pointing

downward, a precipitate. When nothing is removed, as when the products formed by mixing two solutions are soluble, the double

arrow

is

often used

(cf.

242).

An 103. Quantitative Meaning of Equations. equation stands for a reaction not only qualitatively, but quantitatively, that is, it represents not
only what substances are taken and produced, but
their proportions, by weight. We give this quantitative meaning to the equation by letting the symbol represent not only the element in general,
also

but also an atom of it. Then, since each element has a definite atomic weight, the symbol means, also, an atomic weight of the element. Finally, since our common unit of weight, in Chemistry, is the gram, the symbol is allowed to represent a gramatomic Weight of the element, i. e., as many grams of
it

as there are units in

its

atomic weight.

Thus, the

stands for oxygen, for an atom of oxygen, symbol for an atomic weight of oxygen, and for a gram-

atomic weight of oxygen,

i. e.,

16 grams.

MULTIPLES OF SYMBOLS.
If

89

the symbol represents the things named, for the atom, then the formula of a compound represents
corresponding things for the molecule of the compound. The formula NaCl thus stands for a molecule

a molecular weight of it (amounting to 58.5, the sum of the atomic weights 23 and 35.5), and a gram-molecular weight of it (58.5 grams), i. e., as many grams of it as there are units
of
chloride,

sodium

in the molecular weight.


In accordance with these assumptions regarding symbols and
formulas the equation,

Na+HaQ
means that one atom
of

NaOH+H T

to give one molecule of

sodium reacts with one molecule of water sodium hydroxide and one atom of hydro-

gen. If the symbols stand for gram-atomic weights (and they do), the equation also means that 23 grams of sodium (see the list of atomic weights in 97 and in the Appendix) react with 18
(i. e., 2+16) of water to give 40 grams (i. e., 23+16+1) sodium hydroxide and i gram of hydrogen. Of course the proportions will be just as true for pounds, tons, or milligrams

grams
of

as for grams.

In 104. Multiples of Symbols and Formulas. the formula for water (H 2 O), the small mimeral, 2,

and slightly below, the H, means two atoms and two atomic weights, of hydrogen. A numeral so
after,
y

placed

multiplies
it.

only

the

symbol

immediately

preceding

90

EQUATIONS AND NOMENCLATURE.


figure before a

weight in the formula.

formula multiplies every atomic Thus, the equation,

Zn+2 HC1
means that an atom

ZnCl2 +2

of zinc reacts with

two molecules

of hydrochloric acid to give one molecule of zinc chloride and two atoms of hydrogen. It also means

that 65 grams of zinc act

upon 73 grams

(i. e.,

[1+35.5]) of hydrochloric acid to give 136 grams (i. e., 65+2X35.5) of zinc chloride and 2 grams of

hydrogen.
105. Radicals.
It often

happens that a formula

contains a group of elements repeated two or more times. Thus, the formula of calcium hydroxide is

Ca(OH) 2
still,

it

may

also

be written
first

CaO

or,

better
viz.,

CaTT.
,

OTT

In the

of these formulas,

Ca(OH) 2

the small figure written after the parenthesis

multiplies

what

preceding, just as

were

together

parenthesis immediately the symbols in the parenthesis one symbol. Symbols which are
if

is

in

the

grouped together in
Thus,
all

this

way
is

are called radicals.

OH. Sodium hydroxide Fe(OH) 3 All nitrates have the radical NO 3 e. g., NaN0 3 Cu(N0 3 ) 2 and Fe(N0 3 ) 3 All sulcontain the radical e. Na SO CaSO and 4 2 phates 4 g., S04, Fe 2 (S04) 3 The formulas of the cupric nitrate, Cu(NO 3 ) 2 and the ferric sulphate, Fe 2 (S04) 3 might be written CuN 2 Oe and Fe 2 S3 Oi2, respectively, but the first formulas are preferable
hydroxides contain the group
ferric
is

NaOH, and
,

hydroxide
,

WRITING EQUATIONS.

91

because they enable us to see that the compounds are derived

from

nitric acid

and sulphuric

acid,

HN0

and

H SO
2

4,

respec-

tively, while the

second formulas do not.

1 06.

Writing Equations.

ing unless they are the result of experiment.

Equations mean nothIf the

student himself cannot prove what products are formed in a reaction, he must depend upon some trustworthy source, e. g., the teacher or a text-book,
for the information.

When

the factors and products

known, the equation may be written. Thus the union of iron and sulphur to form ferrous sulphide (cf. 10), the burning of magnesium in oxygen
are
(cf.

24),

by heat

and the decomposition of mercuric oxide 16 and 22) are represented by the (cf.

equa/tions,

Mg+0
HgO

MgO; Hg+0.

When

sulphur
(cf.

is

burned

in air the product is sulphur

dioxide

257).

The

simplest equation would be,

s+o
This equation
is

so 2

qualitatively

correct;

that

is,

it

represents factors and products.

however, two atomic for it shows weights quantitatively correct, of oxygen in the product, and only one as a factor.

It is not,

The

correct quantitative equation

S+2

is,
.

S0 2

92

EQUATIONS AND NOMENCLATURE.

Changing the simplest equation into a quantita" the " equabalancing tively correct one is called tion. The three equations already given do not
require balancing.
For the decomposition of potassium chlorate by heat the simplest equation is,
(cf.

19;

KC10 3
The
balanced equation
is,

KC1+0.
>

KC10 3
The simplest equation
zinc
(cf.

KC1+3

0.

for the action of hydrochloric acid

upon

47)

is,

Zn+HCl

>

ZnCl 2 +H.

This equation cannot be balanced by changing the formula ZnCl 2 to ZnCl, for 65 parts of zinc unite with 71 parts of chlorine, as

shown

in the formula

ZnCl 2

The balanced equation


>

is,

Zn+2 HC1
107.

ZnCl 2 +2 H.
of

The
(cf.

Crystallization. water of crystallization present in a hydrate 88) is represented by the formula of water

To Represent Water

(taken the necessary

number

of

times)

after

the

formula of the anhydrous substance. A period is Thus, while CuSO 4 stands placed between them.
for

anhydrous
is

copper

pentahydrate,
(white
vitriol)

CuS0
.

4.

sulphate, blue vitriol, its The zinc sulphate 5 2 O.

obtained from

water solution has

the formula ZnS0 4 7 and Glauber's salt, the 2 O, 2 0. decahydrate of sodium sulphate, is Na^SCX. 10

108. Calculations

formula

of

From the from Formulas. a compound we can calculate the per cent

CALCULATIONS FROM FORMULAS.


of each of the elements

93

composing it. We get the atomic weights from the lists ( 97 and Appendix). We calculate the percentage composition of water,

H O,
2

as follows

2X1,
or

The hydrogen The oxygen

(2 gram-atomic weights) weighs


(1

2
16

g. g.

gram-atomic weight) weighs 1X16, or

The gram-molecular weight of water = The hydrogen is -&, or 11.11%. The oxygen is U, or 88.89%.

18

g.

In the same

way we

calculate

the percentage

composition of aluminum oxide, A12 O3.


2
g. at.

wts. of Al weigh

2X27, or

54

g.
g.

g. at.

wts. of

weigh

3X 16,

or

48

Hence the gram-molecular weight of A1 2 3 = 102 g. Therefore the aluminum is AV, or 52.94%,

And

the oxygen

is

iVV, or 47.06%.

The per cent of water of crystallization may be calculated from the formula of the hydrate. Thus, from the formula of blue vitriol, CuS0 4 5 2 O, we
.

calculate as follows:
1 g. at.

wt. of

Cu

weighs

63
or

g. g.

1 g. at.

g.

wt. of S weighs at. wts. of weigh

4X 16,

32 64
is

g.

The gram-molecular

wt. of anhydrous cupric sulphate 5 gram-molecular weights of water weigh 5X 18, or

159

g. g.

90 249

The gram-molecular weight

of blue vitriol

is

g.

Therefore the water of crystallization

is

-/&, or 36.14%.

94

EQUATIONS AND NOMENCLATURE.


109. Calculations

equation for a reaction

from Equations. From the we can calculate the proportions, by weight, in which the factors must be present, and the relative amounts 6*f the products.
Thus, the equation for the preparation of hydrogen

from zinc and dilute sulphuric acid

(cf.

47)

is,

Zn+H S0
2

ZnS0 4 +2 H.

The proportions by weight the symbols and formulas


:

may

be written under

Zn
65

H S0
2

ZnS0 4
161
g.

+2

H.

+(2+32+64) 98 g. 65g.+

(65+32+64) +2.

+2g.

According to this equation, 65 grams of zinc react with 98 grams of sulphuric acid to give 161 grams of
zinc sulphate

and 2 grams

of hydrogen.

Suppose, now, we wish to know how much sulphuric acid is needed to react exactly with 40 grams of zinc. Since 65 grams of zinc require 98 grams of sulSolution.
phuric acid for complete action (see equation), 40 grams of zinc will require This 98, or 60 grams of sulphuric acid.

MX

is,

of course, the least quantity of sulphuric acid that will use


all

up

of the zinc.

If

a larger amount

is

used, the excess will

simply remain in the solution.


for
of zinc sulphate formed may also be calculated, 65 grams of zinc give 161 grams of zinc sulphate, then 40 grams of zinc will give If X 161, or 99 grams of zinc sulphate.

The quantity
if

The amount
or 1.2 grams.
If

of the

hydrogen produced

is,

evidently, if

X 2,

we wish

grams

of hydrogen,

to find the weight of zinc needed to produce 5 we solve as follows


:

HOW A COMPOUND
Two grams
of

IS

NAMED.

95

zinc used up, hence to produce 5 |X65, or 162.5 grams, of zinc.

hydrogen are produced for every 65 grams of grams of hydrogen will require

Suppose the problem


produce,

by

its

hydrogen at

"How much zinc is required to is: action with dilute sulphuric acid, 40 liters of " C. and under 760 mm. pressure?
find the

We

must

first

weight

of the hydrogen,

and then

cal-

culate the weight of the zinc necessary. The weight of 40 liters of hydrogen under the conditions

given is 40X0.09, or 3.6 grams. Since 65 grams of zinc produce 2 grams of hydrogen, the weight of zinc needed to yield 3.6 grams 6 of hydrogen is X65, or 117 grams. If the volume of the

hydrogen were measured at some other temperature and pressure, the first operation would be to reduce the volume (c/. 44) to standard conditions, for the weight of a liter (0.09 gram)
applies only under standard conditions.

10.

How a Compound of Two Elements is Named.


of the

- Most
binary

compounds we deal with have two

or three elements.

We

call

those having only two,

compounds; those having three, ternary compounds. The name of a binary compound contains the names of both its elements, but the last syllable of one of them is changed to ide.
Thus sodium
magnesium
before the ide
is

chloride is

oxide,

a compound of sodium and chlorine; one of magnesium and oxygen (here the y omitted); calcium carbide, one of calcium and

carbon; lead sulphide, one of lead and sulphur.

Most binary compounds contain a metal and a non-metal (cf. 8), and it is the ending of the nonFor purposes of metal that is changed to ide.

96

EQUATIONS AND NOMENCLATURE.

hydrogen is usually considered a in as hydrogen sulphide and hydrogen phosmetal, But its compounds with metals are called phide.
nomenclature,
hydrides.
All binary

compounds

of

oxygen are

oxides.

in. Naming

of Different

Compounds

of the

Same

Two

If there are two compounds of Elements. the same two elements we distinguish between them

as follows:
(1)

change the
final syllable of the
ic
;

We We

name

of

the first element to ous or


(2)

or

place a prefix, usually a numeral or per, before the name of the second element.

The ending ic is given to the first element in the compound having the larger proportion The ending ous is used in of the second element. the compound having the smaller proportion of the
case of the

second element.

HgCl and HgC^, are

Thus, the two chlorides of mercury, called mercurous chloride and

mercuric chloride, respectively.


For some elements, e. g., copper and iron, the Latin names are Thus we have the names cuprous oxide and ferrous

used.

chloride for the

compounds having the smaller proportion of non-metal, and cupric oxide and ferric chloride for the compounds having the larger proportion of non-metal.

The second method


is

of

naming binary compounds

numeral prefix before the second element. Thus, we have the names carbon monoxide and carbon dioxide for the substances CO and CO 2
to use a
,

EXERCISES.
respectively,

97

and the names sulphur dioxide and sulphur trioxide, for the compounds S0 2 and SOs,
respectively.
112. Exercises.
advantages can you see in using the formulas NaCl, PbS, and NaOH, for the substances salt, water, galena, and caustic soda, respectively? How does the equation for the " chemical reaction between sodium and water ( 102) show that
1.

What

H 0,
2

" action consists in changes in the relations of elements ( 92)? 2. Give the origin and meaning of the terms symbol, formula,

equation, qualitative, quantitative. 3. Give the source of the symbols for sodium, potassium,

mercury, iron, copper, silver, gold, lead. Carbon 4. What are the molecular weights of the following monoxide, carbon dioxide, sulphur dioxide, alcohol (C 2 6 0),
:

glycerine
5.

(C H
3

3 ),

and potassium chlorate?


chlorate,

Calculate the percentage composition of the following:


sulphuric acid,

Carbon dioxide, alcohol, potassium sodium hydroxide.


6. If

dilute

the equation for the reaction between magnesium and 2 S0 4 MgS0 4 +2 T calsulphuric acid is

Mg+H

how much hydrogen can be obtained magnesium are used. How much magnesium much sulphuric acid is necessary?
culate
7.

if

10 grams of

sulphate?

How

Calculate
salt,

the

per

cent of

water of crystallization in
.

gypsum, CaS0 4 2 H 2 0. 8. How many grams of phosphorus must be burned to produce 60 grams of phosphorus pentoxide, P2 5 ? 9. Name the compounds having the formulas CO, Pb0 2 SrCl 2 SnCLt, Hgl, HgI 2 and BaC 2
Glauber's

white

vitriol,

and

in

CHAPTER

IX.

CHLORINE.
Chlorine is a heavy, greenish113, Occurrence. of irritating odor and poisonous properyellow gas,

was discovered by the Swedish chemist Scheele in 1774, but was not generally considered to be an element until 1809.
ties.

It

Because of its great reactivity, i. e., its tendency to act chemically with other substances, chlorine is not

found in nature free, but always in combination with other elements. Its most abundant compounds are
sodium, potassium, and magnesium chlorides and
hydrochloric
acid,
is

which

is

hydrogen

chloride.

Sodium
114.
is

chloride

common

salt.

Common Method

usually prepared

chloric acid
is

by manganese upon

of Preparation. Chlorine the action of reagent hydro-

dioxide.

The apparatus
in small

shown

in Fig. 29.

A
is

flask containing

manganese dioxide (Mn02)

lumps

provided with a thistle tube and a delivery tube, and is supported so that it may be warmed in a water bath. Concentrated
hydrochloric acid is added through the thistle tube, and the evolution of chlorine begins. The gas is allowed to pass through a drying bottle one-third full of concentrated sulphuric acid
(a

U-tube

of calcium chloride

may

be used instead), and then

STUDY OF THE REACTION.

99

into a collecting bottle, the air of which is to be displaced by chlorine. From the collecting bottle a delivery tube reaches

beneath the surface of a


solution
of

droxide,

sodium hywhich absorbs

any

When

chlorine. escaping the gas is com-

pletely soluble in

sodium
that

hydroxide we know
has been displaced. a collecting bottle
of chlorine
it

the air in the apparatus

When
is

full

removed and stoppered, and replaced by another bottle until enough gas has been
is

FIG. 29.

obtained.
of

The
is

evolution

chlorine

stopped by

filling

the

flask

with cold water.

115.

Study

of the Reaction.

manganese dioxide and hydrochloric more complex than the reactions hitherto studied. The manganese dioxide reacts like manganous oxide and oxygen (MnO +0) If manganous oxide were to react with hydrochloric 92) giving manacid, a double decomposition would occur (cf. ganous chloride and water:
reaction between acid
is
.

The

MnO+2 HC1

MnCl

+H 0.
2

Oxygen, alone, reacts with hydrochloric acid, giving water chlorine:

and

0+2 HC1

2 Cl

+H 0.
2

The complete reaction would, therefore, be represented ing the equations for the partial reactions:

by add-

Mn0 +4 HC1
2

MnCl 2 +2 Cl+2

H 0.
2

100
Since the oxygen
its
is

CHLORINE.
not actually formed, it is best to enclose This indicates that it is an inter-

symbol

in a parenthesis.

mediate product.
(1)
(2)

The
2

partial equations thus

become

Mn0 +2HCl
(0)+2HC1

>MnCl
2

+H 0+(0).
2

>H 0+2C1T.
is

When

the intermediate product (0)


is,

eliminated, the

sum

of these partial equations

as before,

Mn0 +4 HC1
2

MnCl 2 +2 Cl+2
acid.

H 0.
2

The
is

second of the partial equations shows us that the chtofine


138.

formed by the oxidation of hydrochloric For another view of the reaction, see

Instead of manganese dioxide and hydrochloric acid we may use common salt, manganese dioxide, and sulphuric acid. The reaction is practically the same, however, for the salt reacts with
the sulphuric acid to give hydrochloric acid (cf. 126), and this The stages of the reacreacts with the manganese dioxide.
tion are

shown
(1) (2) (3)

in the following partial equations:

NaCl+2
2
2

H S0
2 4

Mn0 +H S0
(2

2 NaHS0 +(2 HC1). MnS0 +H 0+(0).


4 4
2

HC1) + (0)
is,

>

H 0+2 Cl t
2

The complete equation


2
2 2

NaCl+Mn0 +3 H S0
Cl
T
.

>

NaHS0 +MnS0 +2 H O
4
4

+2

116.

Other

Methods.

Manganese

dioxide

is

not the only substance that will liberate chlorine

from hydrochloric acid; potassium K2 Cr2 O 7 potassium chlorate, KC10 3


;
;

dichr ornate,
nitric
4,

acid,

HNO

3,

potassium permanganate, KMnO


it.

and many

other substances will do

THE ELECTROLYTIC METHOD.


But potassium

101

chlorate and hydrochloric, acid give, besides an chlorine, explosive oxide of chlorine. Similarly the chlorine formed from the action of nitric acid upon hydrochloric acid is mixed with other substances. Hence these methods are not used

to prepare gaseous chlorine.

The mixture

of nitric

and hydrochloric acids

is

used extensively, however, under the name aqua regia (i. e., royal water) as a solvent for gold, platinum, and other metals not readily attacked by single
acids.

acid

called, also, nitro-hydrochloric regia thus only a source of chlorine. Metals dissolved in it are converted into chlorides.
is

Aqua

It will be noticed that the substances which react with hydrochloric acid to give chlorine are all oxidiz-

The liberation of chlorine in all the ing agents. methods described is thus brought about in pracone way, namely, by the oxidation of the hydrogen of hydrochloric acid to water, the chlorine
tically

being set

free.

HC1+O

H 0+2 Cl
2

In Deacon's Process crude chlorine is made on a large scale by the use of atmospheric oxygen as oxidizing agent. Hydrogen chloride mixed with air is passed over heated bricks which have been soaked
in copper sulphate or copper chloride solution. In the presence of these catalytic agents the oxygen of

the air acts like the oxidizing agents

named

above.

The

Electrolytic

Method

of

making

chlorine con-

sists in electrolysing

a concentrated solution of hydro-

102
chloric acid or of

CHLORINE.

sodium

chloride.

The

chlorine,

which

electro-negative, appears at the positive electrode, and the metal or hydrogen at the negative electrode (cf. 61).
is

Chlorine is about 2| 117. Physical Properties. times as heavy as air, and 35.5 times as heavy as

hydrogen.

It is easily soluble in water,

more than

two volumes

of the gas being absorbed

water at the ordinary temperature.

by one of The solution


of

called

chlorine

water

possesses

many
salt,

the

properties of the gas.


In a warm, saturated solution of
only slightly soluble;
instead of under
air.
it

common

chlorine

is

may, therefore, be collected over brine

solution

is passed into iced water and the cooled below C., a crystalline substance separates out; this is a compound containing

If

chlorine
is

144 parts of water to 71 of chlorine, and therefore It is called 2 0. represented by the formula C1 2 8
.

chlorine hydrate. Use may be made of this substance to condense chlorine to the liquid state.
For
tals

this purpose, the crys-

of

chlorine

hydrate are
papers or
plates,

dried between

filter

on unglazed clay

and

then put into the closed limb of a tube bent as shown in The open end is Fig. 30. then sealed.

FIG.

so.

The end

of the
is

tube containing the chlorine hydrate

now warmed

in a water

CHEMICAL PROPERTIES.
bath to 30
mixture of
its

103

C., while the other


ice

end

is

surrounded by a freezing

After a short time, liquid chlorine will condense at the drawn-out end. The gas has been liquefied by
salt.

and

own

pressure.

This experiment can be carried out only

in

strong tube securely sealed.

Liquid chlorine
stored
118.

is an article of commerce; and transported in iron cylinders.

it

is

Chlorine is a very and to substance inhale,. should, therefore, dangerous be generated only hi a gas chamber, or where there is a good draught. If it has been taken into the lungs,
alcohol or
it.

Chemical Properties.

ammonia should be

inhaled to counteract

It is

always well to sprinkle a

little

ammonia water about

in

the neighborhood of a chlorine generator.

Chlorine
chlorides.

is

intensely active toward

many

other

elements, forming,

by

direct union with them, the

Many

substances

that

combine

with

oxygen slowly, or not at all at ordinary temperatures, unite readily with chlorine. Powdered antimony

and copper foil (the latter must be hot) glow when put into chlorine, the products being antimony trichloride (SbCl 3 ) and cupric chloride (CuCl 2 ) reSodium, tin, magnesium, and phosspectively. phorus all give corresponding chlorides when put into the gas. But it is toward hydrogen that chlorine shows its most remarkable behavior, for while the two gases do not combine at all in the dark, and

104

CHLORINE.

only very slowly in diffused light, yet they unite with explosive violence in sunlight.

The mixture

of

hydrogen and chlorine

may

also

be exploded

by a burning match or by the

electric spark.

Chlorine shows this tendency to combine with hydrogen not only when the hydrogen is in the free
state,

but also when

it is

united with other elements.


the action of chlorine

As

illustrations

we may take

toward water, ammonia, and turpentine.


119.

Action of Chlorine

Oxygen

and Water.
ous
solution

The aqueof

chlorine

Chlorine

Water

may be preserved for a long time if kept cold and in the dark, but it decomposes rapidly in sunlight, giving as final products hydrochloric acid and oxy-

J
(1) (2)

llorine

Water

Fm.31.

The stages gen reaction are: .

of

the

H 0+2
2

Cl

HOC1

HOC1 + HC1 HC1+OT.


is,

(cf.

329).

The complete
2

reaction

H O+2
If

Cl
is

HC1+O T

the decomposition

(Fig. 31),

oxygen

will collect in

carried out in a long tube the upper part of the

tube.

USES OF CHLORINE.
1 20.

105

Action of Chlorine and Ammonia.

When

the hydrogen of ammonia is appropriated by chlorine, hydrochloric acid and nitrogen are formed, as repre-

sented

by the equation,

NH +3
3

Cl

HC1+N.
the hydrochloric acid the material of
chlorine

With the
gives the white

excess of

ammonia

ammonium

chloride,

NH C1,
4

smoke seen when ammonia and


together.

gases

come

121. Action

of

Chlorine

The behavior of chlorine shown by immersing a piece

and Hydrocarbons. and hydrocarbons may be


of filter

paper in

warm

turpentine and then plunging it into a jar of chlorine. The turpentine soon ignites, and burns with a smoky The' chlorine unites with the hydrogen, flame. and sets carbon free.

Ci

16

+16
of

Cl

16

HC1+10 Cl.
Chlorine
is

122.

Uses

Chlorine.

used

in

large quantities as a bleaching


It is

and

disinfecting agent.

not used
"

directly,

but

is

converted into bleaching

powder, or

chloride of lime."

Bleaching powder
"

is

formed by the action

of chlorine

lime (calcium hydroxide), and is by acids, even by the carbon dioxide of the
the formation of hypochlorous acid,

upon easily decomposed


air,

slaked

"

with
329)
.

HOC1

(cf.

106
This
is

CHLORINE.

decomposed

readily, giving

oxygen in an

exceedingly active (nascent) condition.

HOC1

>

HC1+0.

Fabrics to be bleached are, therefore, immersed alternately in baths of dilute acid and of chloride of
lime.
tact

In this

way oxygen

is set free

in immediate con-

with the coloring matter of the


is

cloth,

and

bleaches

it.

Chlorine
present.

not a bleaching agent ordinarily, unless water


is

is

The bleaching

bleaching powder,

action of chlorine water, like that of due to hypochlorous acid (cf. 119) and

oxygen.

Compared with the old bleaching process, which consisted in exposing the fabric to the oxidizing agents of the air, the chlorine method is of course very rapid, but, unfortunately, the bleaching agent used too often attacks the fiber of the cloth as well as its
coloring matter.

Hence

delicate materials, such as the better

grades of straws, laces,

silks,

and woolens, are usually decolorized

dioxide, which, although it does not bleach so permanently, has yet the advantage of acting less upon the fabric.

by sulphur

The
its

action of chloride of lime as a disinfectant

is

similar to

action as a bleaching agent: nascent oxygen is formed, this destroys the micro-organisms of the surrounding air.

and

Nascent State. We have just seen that as set free from bleaching powder and from chlorine water, is very active, and able to effect changes impossible under ordinary conditions.
123.

oxygen,

We
tion

say
is

it is

in a nascent state.

The nascent

condi-

due either to the presence of catalytic agents, in contact with which the active element is liberated,

EXERCISES.
or to the energy given off

107
it

when

is

set free

(c/.

27 and 312).
124. Exercises.
1.

How many
by the

grams

tained

electrolysis of

of chlorine can, theoretically, be ob50 grams of hydrochloric acid?

2. How many grams of manganese dioxide are required to give with an excess of hydrochloric acid 10 grams chlorine? 3. How many liters of chlorine are needed, at 30 C. and 760

mm., to convert 12 grams PC13 ?

of phosphorus into the chloride,

4. How much silver chloride, AgCl, can be formed by burning 54 grams silver in chlorine gas? 5. Calculate the per cent of chlorine in sodium chloride.
6.

How many

liters of

chlorine can be

made by

the action of

25 grams of manganese dioxide with an excess of hydrochloric acid? (Assume that 1 liter of chlorine weighs 3 grams.)

CHAPTER

X.
ACID.

HYDROGEN CHLORIDE AND HYDROCHLORIC


125. Occurrence.
less,

Hydrogen

chloride

is

a color-

heavy gas that fumes

in moist air,

and

dissolves

readily in water. It is found in only small amounts in nature, e. g., in volcanic gases and in some springs. of the gastric juice. It makes up about 0.22 of

1%

The
"

aqueous
"

solution

is

hydrochloric

acid,

or

muriatic

acid.

126. Preparation, (a) Common Laboratory Method. Hydrogen chloride may be made by the action

of sulphuric acid,

H SO4,
2

upon common

salt,

NaCl.

The apparatus is like that for The flask contains salt and
with half
its

chlorine (Fig. 29). sulphuric acid diluted

In

of water, and cooled. (Caution ! diluting sulphuric acid always pour the acid into

volume

the water.)

small flame or hot-water bath

is

used

to heat the flask.

The

first

bottle contains con-

centrated sulphuric acid to dry the gas, and the second bottle is for collecting it. A beaker of water
collects any gas that would escape. When the gas bubbles in the beaker are completely soluble, we

know

that the collecting bottle


108

is

free

from

air.

PREPARATION.

109

The equation

for the reaction


2

is,
4
.

NaCl+H SO
(b)

NaHSO +HCl T
is

Commercial Manufacture.
hydrogen
chloride

On a commercial
in a retort like that

scale

made

shown
s

" " in Fig. 32. The pan is of cast-iron, about 10 feet in diameter, and inclosed in brick. There

a furnace below

it,

and a

side door through

which

FIG. 32.

can be put in. The charge consists charge of a ton or more of salt, and the amount of sulphuric
the

"

"

The
off

acid necessary to produce sodium sulphate, Na2 SO 4 first stage of the reaction is shown in the equa.

The hydrogen chloride is conducted forming commercial hydrochloric acid. When the mass in the " pan " is pasty it is raked over into the " roaster," where it is heated to red heat. The second stage of the reaction then
tion given in (a) into water,
.

takes place

NaCl+NaHS0

Na SO +HCl T
2

110

HYDROGEN CHLORIDE,

The sodium sulphate is used in the manufacture of (cf. 418). Hydrogen chloride is also a in of soda ( 414) by the manufacture by-product
glass, etc.

the Le Blanc process. It is evident that the hydrogen of sulphuric acid, like that of water, may be replaced in two stages; for

while at low temperatures only 58.5 grams of sodium chloride react with 98 grams of sulphuric acid, at a

high

temperature

second
first, is

quantity

of

chloride, equal to the

able to react,

sodium and thus

produces a second quantity of hydrogen chloride. This will be more evident when the two equations
are written together
(1)
:

(2)

NaCl+

> S0

> S0
Hydrogen

+HC1.
chloride
is.

127. Physical Properties.

about 1} times as heavy as air, and 18} times as heavy as hydrogen. It is very soluble, 505 c.c. being held by 1 c.c. water at C. and 760 mm. pressure.
solution of the pure gas in distilled water at the ordinary temperature is the " chemi"
cally
is

The concentrated

This (c. p.) reagent hydrochloric acid. pure a colorless liquid of specific gravity 1.2, which fumes strongly in moist air because the escaping

gas condenses the water-vapor.

An
off

aqueous solution of hydrogen chloride gives


if

the gas,

concentrated, or water,

if

dilute, until

VOLUMETRIC COMPOSITION.
the concentration
is

Ill
chloride.

20.2%
C.

of

hydrogen

Then

it distills

at 110

The dry gas can be converted into a colorless liquid at a low temperature and great pressure.

Hydrogen ChloThe composition of hydrogen chloride may be demonstrated in the same way as that of water,
ride.
viz.,

128. Volumetric Composition of

by

electrolysis. If

an

electric

current of

suffi-

cient

strength is passed through a concentrated

aqueous solution of the acid, hydrogen is produced at the electrode,

and chlorine at
electrode.

the

The

gases collect at unequal

rates, at first,

because of the
FIG.
33.

greater solubility of the chlobut when the liquid has rine


;

become saturated with both gases the hydrogen and the chlorine gather in the collecting tubes at the same rate. See Fig. 33.

Therefore, hydrogen chloride must be composed of hydrogen and chlorine united in equal proportions

by volume.

The same
if

it

be proved synthetically, for a mixture of hydrogen and chlorine be exploded, will be found that equal volumes of the two gases
fact

may

112

HYDROGEN CHLORIDE.

have disappeared. The volume of hydrogen chloride formed will be equal to the sum of the uniting gases. These facts may be represented graphically as
follows:-

D
1 vol.

D
1 vol. chlorine.

>

CD

hydrogen.

2 vols. hydrogen chloride.

Note that this case is different from that of water; for, in the production of 2 volumes of steam, 2 volumes of hydrogen united with 1 of oxygen, i. e., 3 volumes of the mixed gases, gave only 2 volumes of the product.

chlorine are about as 1

Since the weights of equal volumes of hydrogen and 35.5, the two volumes of
:

hydrogen chloride formed by their union should be about 36.5 times as heavy as one volume of hydrogen.

Hence hydrogen

chloride

should be about

18.25
is

= 36.5-:-2) (

times as heavy as hydrogen.

This

actually the case.

That hydrogen chloride

gives,

HCl

when decomposed, one-half of its own volume of hydrogen, may be shown by the action of sodium. _
.

,.

.bor

convenience

the
it

sodium

is

diluted

by
is

alloying

with mercury.

Hg.

amalgam

FIG.

34.

of the resulting sodium put into a long measuring tube (Fig. 34) full of hydrogen chloride. The open end of the tube is then closed with the thumb, and the tube is shaken vigorously. When the thumb is removed under

small

amount

water,

some

of the

water rushes up into the tube to replace the

CHEMICAL PROPERTIES.
chlorine.
If

H3
is

the water inside and outside the tube


level,

now brought

the volume of the residual hydrogen will be found to be approximately one-half that of the hydrogen chloride
to the

same

taken.

Chemical Properties. When 1 gram of chlorine unites with the heat liberated hydrogen is 22,000 calories, consequently hydrogen chloride It does not react with most is very stable (cf. 27) non-metals, but is oxidized by the air in the presence
129.
.

(cf. 116), giving chlorine. The moist water solution are acids. Acids may be described roughly as having a sour (acid) taste, the

of catalyzers
its

gas and
ability

to

change certain vegetable

colors,

e. g.,

blue or purple litmus to red,


neutralize

and

also the

power to

the properties of another class of sub-

stances, viz., the bases. Thus the action of hydrochloric acid upon sodium hydroxide (a base) gives

sodium chloride (common salt) and water. Metals, too, react with acids, forming salts. Thus, zinc with
hydrochloric acid gives zinc chloride
(a salt)

and

hydrogen.
These reactions are shown in the equations,

NaOH+HCl
Zn+2 HC1
Hydrochloric acid
acids.
It
is is

NaCl+H 0,
2

and

ZnCl 2

+H

2.

made on a

one of the most important large scale, and is used

in

enormous quantities to prepare chlorine and

chlorides.

114

HYDROGEN CHLORIDE.

-- The chlorides 130. Chlorides. may all be considered hydrogen chloride with its hydrogen replaced by a metal. The most important chlorides have been
given in
113;

others are

barium
of

AgCl, and most abundant chloride NaCl.


silver chloride,

ferric
is,

BaCl 2 The chloride, common course, salt,


chloride,
,

FeCl 3

The
water.

chlorides of

most

of the
silver

common
chloride,
,

metals are soluble in

Exceptions are

chloride,

HgCL Lead

chloride,

PbCl 2

is

AgCl, and mercurous only slightly soluble in

cold water,

but more readily in hot water.

When, therefore, solutions of salts of silver, lead, and mercury (in its mercurows condition) are treated
with a solution of a chloride, the chlorides of these metals are precipitated.
131. Exercises.
1.

300

c.c. of

hydrogen and 250

c.c.

of chlorine
Its

and exploded.
of the gases used
2.

What was
was

the product?

were mixed volume? Which

in excess?

How much?

Calculate the percentage composition of hydrochloric acid. 3. How many grams of sodium chloride are needed to yield,

with sulphuric acid, 20 grams hydrogen chloride? 4. How many grams hydrogen chloride can be made from 35

grams potassium
5.

chloride,

KC1?

weight of sodium chloride is necessary to produce, with sulphuric acid, 20 liters of hydrogen chloride at 20 C. and 800 mm. pressure?
6. How many liters of hydrogen chloride can be made, at 40 C. and 650 mm., by heating 117 grams of salt to red heat with an excess of sodium hydrogen sulphate?

What

CHAPTER

XI.

VALENCE.
132. Meaning of Valence. chlorides (Chapters IX and
differences.

The formulas of the X) show important

While in sodium chloride (NaCl) each is combined with one chlorine atom, in calcium chloride (CaCk) one atom of calcium holds two atoms of chlorine. In antimony chloride (SbCl 3 ) the relation is 1 to 3, and in platinum chloride (PtCl 4 )

sodium atom

it is 1

to

4.

Similar differences appear in hydrogen

compounds,

Hydrogen
Water,
chloride,
2
;

C1H;
3
;

OH
(

Ammonia
Marsh gas

203),
(

NH

291),

CH

4.

This ability o/ the atoms

to

unite with different

num-

bers of other atoms is called valence.

of Valence. --The direct measure an element in any compound is the number of hydrogen atoms with which one atom of Since the hydrogen atom the element combines. is never found in combination with more than one atom of another element, it is said to have a valence

133.

Standard

of the valence of

of

i,

or to be univalent.

The valence
115

of chlorine in

116
the chlorides

VALENCE.

In water, the two hydrois, likewise, i. with a total valence of 2, hold one atom gen atoms, The valence of the oxygen atom is, of oxygen. therefore, 2, or it is bivalent. The atom of calcium is also bivalent, for it is combined with two atoms The nitrogen of ammonia of univalent chlorine. has a valence of 3, or is trivalent; so is antimony
in

antimony

chloride.

Platinum and carbon have a


in platinum chlo-

valence of 4
ride

are quadrivalent
gas,

and marsh

respectively.

In phosphorus

pentachloride (PC1 5 ) phosphorus is quinquivalent. Sometimes the Greek numeral prefixes are used, as
in divalent, tetravalent, and pentavalent. The valence of elements is often represented

by
to

small

Roman numerals
1 ,

placed a

little

the right of the symbols. Thus Al means trivalent univalent mercury; and Pt lv aluminum; Hg
,

above

and

quadrivalent platinum.

The valence of 134. Valence by Replacement. an element is measured not only by the number of hydrogen atoms with which its atom has combined,
but also by the number

sodium

is

it has replaced. Thus univalent in sodium hydroxide (NaOH), it

because one atom of

has replaced one of the hydrogen atoms of water (HOH). In calcium hydroxide, Ca(OH) 2 calcium is bivalent: its atom has replaced two hydrogen atoms (of 2 HOH). The formulas of the sulphates of these two elements (Na2SO 4 and
,

CaSO

4)

also

show

their valences, for while

it

takes

FORMULA TYPES.

117

only one bivalent calcium atom to replace the two hydrogen atoms in the molecule of sulphuric acid
(H^SCX),
it

takes two atoms of univalent sodium.

135. Valences of

Some Elements and

Radicals.

118

VALENCE.

element, equals valence Xnumber of atoms, in the case of the other.

Thus, an atom of a bivalent element unites with two atoms of a univalent element, as in H 2 O" and Three atoms of a bivalent element unite Ca n m with two of a trivalent one, as in As 2 S 3 and Mg 3 N2
11

III

11

quadrivalent (tetravalent) atom unites with four univalent atoms, as in 4 and SiCl 4 , but with two

CH

bivalent atoms, as in

CS 2 and SiO 2

137. Valence of Radicals.

The

idea of valence applies not only to the atoms of elements,


(cf.

but also to radicals


valence of
i,

105).

Thus the
in

radical

OH

has a

as

in

water
is

(HOH) and
3,

sodium hydroxide

(NaOH).
is

Nitric acid

HN0
SO

hence the
is bivalent,

nitrate radical,

NO

3,

univalent.

The

radical

as in sulphuric acid

(H 2 S0 4 ).
is

Similarly, the radical

_CO 3

of carbonic acid
,

(H 2 C0 3 )

bivalent.

while
If,

SiO 4

hence PO 4 is trivalent, 3 P0 4 Phosphoric acid is the acid radical of silicic acid (H 4 SiO4), is quadrivalent.

therefore,

we wish

to write the formulas of the

compounds

formed by,

us say, magnesium, and these radicals, we apply " " for radicals the valence rule used for atoms, substituting " " atoms (cf. 136). Hence magnesium hydroxide is Mg(OH) 2 the sulphate, the carbonate, MgC0 3 the nitrate, Mg(N0 3 ) 2
let
;
; ;

MgS0

the phosphate,

Mg (P0
3

4) 2

the

silicate,

Mg Si0
2

4.

The idea of valence 138. Multiple Valence. applies only to elements in combination, and not in
the free state.

iron unless

we know
chlorine

Thus, we cannot give the valence of the formula of some iron comis

pound,

If

univalent in the chlorides

MULTIPLE VALENCE.
(and
it is),

119

then iron is bivalent in ferrous chloride If trivalent in ferric chloride (FeCl 3 ). but (FeCl2 ), the then carbon in is oxides, oxygen is bivalent bivalent in carbon monoxide (CO), and quadrivalent in the dioxide (CO 2 ). So phosphorus is trivalent in the formulas PCls and PzOs, but quinquivalent

PC1 5 and P2 5 Sulphur is bivalent in hydrogen sulphide (H 2 S) and all sulphides, quadrivalent in sulphur dioxide, and sexivalent (hexavalent) The element argon (cf. in sulphur trioxide. 191),
(pentavalent) in
.

which forms no compounds,

is

of valence zero (0).

In general, the valence of an element is smaller at high temperatures than at low. Thus, sulphur trioxide breaks up when heated, -

S0 3

S0 2 +0.

Here the valence


heated,

of sulphur falls
also,
is

from

six to four.

Phosphorus pentachloride, PC1 5


T

dissociated

when

PCl 3 +2

Cl.

element may show a higher valence when combined with some elements than with others. This
is

An

shown

in the reaction

by which
MnCl +2
2

chlorine

is

prepared

Mn0 +4 HC1 2

Cl

+2 H 0.
2

is

In manganese dioxide the valence of manganese probably 4 (cj. 341). In a true double decom-

120
position, valences

VALENCE.

do not change; hence we should expect manganese tetrachloride to be formed


:

Mn0 +4 HC1
2

MnCl 4 +2

H 0.
2
:

Instead, we obtain manganous chloride, MnCl 2 the valence of the manganese falls from four to two.
139. Exercises.
1. its

If

the valence of an element


carbonate,

is 1,

write the formulas of

sulphate,

sulphide,

nitrate,

phosphate,

and

Write the formulas of the same compounds of an element, R, having a valence of 2. 2. Give the valence of each element in the following: Li 3 N, Fe 2 S 3 ZnBr2 KI, SrO, As 2 5 SbCl 3 PH 3 Name each of these
nitride.
, ,
,
. ,

substances.
3. -Considering all but the first element in

to be a radical, give the valences of the


radicals:
,

first

each of the following elements and of the


4,

KC10 3

NaN0
.

Fe(OH) 3 Bi(N0 3 ) 3

BaC0 SrS0 A1P0 Name each of these compounds.


3, 3,

4,

Ag3 P0 4?

CHAPTER

XII.

MOLECULAR WEIGHTS.
Combination by Volume Gay-Lussac's Law. have already studied two cases of combination which show that elements unite, not only in definite proportions by weight, but also, if they are The two gases, in definite proportions by volume. cases are, (1) the union of hydrogen and oxygen to give steam (cf. 63), and (2) the combination of with chlorine to produce hydrogen chloride hydrogen The proportions by volume in these 128). (cf.
140.
;

-We

cases are

CD
n
1 vol.

+
1 vol.

D
oxygen.

CD
2 vols. steam.

2 vols. hydrogen.

+
1 vol.

n
oxygen.

en
2 vols. hydrogen chloride.

hydrogen.

The

summarized

facts regarding combination by volume are in Gay-Lussac's Law of Definite Pro-

portions by Volume: The volumes of reacting gases have a definite (and simple) relation to one another

and

to the

Just as elements
unite jn.

Volumes of the products, if these are gases. may unite in more than one
94), so gaseous elements one more than proportion by volume,
(cf.
121

proportion by weight

may

122

MOLECULAR WEIGHTS.

case of hydrogen peroxide and water illustrates this: while two volumes of steam are formed from

The

two volumes of hydrogen and one of oxygen, two volumes of gaseous hydrogen peroxide are composed of two volumes of hydrogen and two of oxygen.

cn
2 vols. hydrogen peroxide.

en
In

en
2 vols. oxygen.

2 vols. hydrogen.

we

141. Avogadro's Hypothesis. "

98 and 99

learned that molecules

hypothesis of
volumes of

Avogadro

is

that

occupy space." The it takes equal numbers


or,

of molecules to occupy equal spaces,


all gases,

that equal

same temperature and contain the same number of molecules. pressure, was an Italian Avogadro physicist, and announced his hypothesis in 1811. Ampere reached the same
at the

conclusion in 1814.
142.

The Molecules

of Elements.

Avogadro's

hypothesis gives us a basis for important deductions regarding the numbers of atoms in the molecules
of gaseous elements.

Let us take the case of hydro-

gen

chloride.

n
1 vol.

n
1 vol. chlorine.

en
2 vols. hydrogen chloride.

hydrogen.

We have no idea how many molecules there actually are in any given volume, but let us assume that there are 1,000 molecules in one volume of hydrogen. Then one volume of chlorine will contain 1,000 molecules (Avogadro's hypothesis), and the two volumes of hydrogen chloride produced will contain 2,000

MOLECULAR WEIGHTS OF GASES.


molecules.

123

But each molecule

of

hydrogen chloride must con-

tain some hydrogen and some chlorine. It cannot contain a whole molecule of either, for there were only 1,000 molecules of

each gas,
1,000 mols.

H+ 1,000 mols.

Cl

2,000 mols. HC1.

Hence, one molecule of hydrogen chloride must contain \ a molecule of hydrogen and \ a molecule of chlorine. Similar reasoning leads to the conclusion that there must be a half-molecuk of oxygen in the molecule of water (steam); for
2,000 mols.

H+ 1,000 mols.

2,000 mols.

H 0;
2

therefore one molecule of steam

must contain one molecule

of

hydrogen and \ a molecule of oxygen. The facts regarding nitrogen are deduced from the equation for the union of nitrogen with hydrogen (cf. 213),

D
1 vol.

+
N.

ECD
3 vols. H. mols.

CD
H

or

1,000 mols.

N+3,000

NH 2,000 mols. NH
2 vols.
3.

3.

of nitrogen

Hence, one molecule of ammonia must consist of | a molecule and 1| molecules of hydrogen.

are

The half-molecules of these four elementary gases assumed to be the atoms, hence we conclude that the molecules of hydrogen, nitrogen, oxygen, and
chlorine consist of two atoms each.
143. Molecular

Weights

of Gases.

Avogadro's

hypothesis is also the basis of molecular weights. We cannot get at the actual weights of molecules,

but we can get at their relative weights, if we assume that there are equal numbers of molecules in equal

124
volumes.

MOLECULAR WEIGHTS.
Thus, since the
liter

of

oxygen

is

practically

16 times as heavy as the liter of hydrogen (-^JP-), the cubic centimeter, and cubic millimeter, of oxygen

must be 16 times as heavy as the cubic centimeter, and cubic millimeter, respectively, of hydrogen. We
conclude,
then,
of

that

the molecule
is

the smallest

oxygen molecule of hydrogen.


gases
is

volume

16 times as heavy as the What is true of these two


the ratio of
the weights of

true of

others:

equal volumes of two gases equals the ratio of their If we assume the molecular molecular weights.

weight of some one gas as a standard, we can find the molecular weights of the others in terms of this
standard.

The atomic weight


142);

of

97); exactly 16 (cf. oxygen molecule (cf.

there are

oxygen is taken as two atoms in the

weight of oxygen

is

taken as exactly 32.


is

hence, the molecular This is the

standard of molecular weights. The molecular weight of a gas from the equation, -

thus determined

Wt. of given vol. of gas Wt. of same vol. of oxygen

Mol. wt. of gas Mol. wt. of oxygen

substituting known values in this equation we can calculate the molecular weight of hydrogen (x)

By

thus:9
1.429

* 32

'
;

whence x = 2.016.

WEIGHT AND VOLUME.


144.

125

Vapor Density Methods.


of

The hypothesis
to liquids

Avogadro applies not only to


can be vaporized.

gases,

but also
liter of

and

solids that

Thus, a

535) is assumed to consteam, or of gaseous acetic acid (cf. tain practically as many molecules as a liter of oxygen under

To get the molecular weights of such sub143. To distinguish the use the stances, equation of methods used for vapors from those used for " " vapor density gases, the former are called
the

same

conditions.

we

methods.
Victor Meyer's

Method. Suppose we wish

to get the approximate molecular weight of

In the method chloroform, boiling at 61 C. of Victor Meyer (Fig. 35) a weighed amount of the chloroform is dropped into the tube
,

and vaporized; the

air

which

is

expelled

through the delivery tube and collected in the graduated tube is a measure of the volume of the chloroform vapor. We thus
obtain the weight of a given number of cubic centimeters of chloroform vapor. By comparing this weight with the weight of an equal volume of oxygen, we can get the molecular

weight of chloroform. The tube A is raised to any required temperature by boiling some liquid in the jacket B;
in the

B
FIG. 35.

case of chloroform, water might be

used.

145.

Gram-Molecular
its

Weight
i. e.,

and Volume. as

We
it

call

32 grams of oxygen,

many grams

of

as there are units in

molecular weightj a gram(cf.

molecular weight of oxygen

103).

For carbon

126

MOLECULAR WEIGHTS.

dioxide (CO 2 ) the gram-molecular weight is 44 grams. The term " gram-molecular weight " is often ab-

breviated to molar weight, or mole. Now, if we determine the volume, under standard

we

conditions, of a gram-molecular weight of oxygen, find it to be 22.4 liters (32 -hi. 429 = 22. 4). The volume of a gram-molecular weight of a gas is called

the gram-molecular volume, and trial shows that the gram-molecular volumes of all gases are the

same,

viz.,

22.4
is

liters.

The gram-molecular

(or

molar) volume

equivalent to the volume of a

cube 28.19 cm. (about 11.1 inches) on each edge. The gram-molecular volume is the basis of a second method of getting the molecular weights of gases we simply determine the weight, under standard conditions, of 22.^ liters of the gas. This gives us the
:

gram-molecular weight.
The method does not differ is shown by the following
Wt. of Wt. of 1
Then, wt. of
of gas.
1
1
1. 1.

in principle

from that of

143.

This

equations:

of gas

~~

of

oxygen

Mol. wt. of gas Mol. wt. of oxygen


of

1.

gasXmol. wt.

= wt.
we

of

1.

OXmol.

wt,

Substituting

known
of
1
1. 1.

values for oxygen

have,

Wt. Wt. Wt.

of 1 of 1

gas X 32 = 1.429 Xmol. wt. of gas; gasX T: || = mol. wt. of gas;

1.

gasX22.4 = mol. wt.

of gas.

FREEZING-POINT METHOD.
146. Molecular

127

Weights of Soluble Substances. of determining molecular methods foregoing not to substances that cannot be apply weights do vaporized. For soluble substances, however, methods

The

upon the properties of the solutions, viz., upon freezing point, the boiling These point, and the osmotic pressure (cf. 149).
methods
depend upon the fact that solids and have many of the properties they would possess if they were gaseous. Solution methods do not apply to acids, bases, and salts (cf. 173).
all

are available that are based

liquids in solution

When sugar is 147. Freezing Point Method. dissolved in water it retards the water molecules in
their

change to the
at

solid state,

hence the solution

freezes

a lower temperature than pure water. Other solutes have a similar effect. Now, we can
substances as

get the molecular weights of such


alcohol

and glycerine (C 3 H 8 3 ) by " vapor 144). The gram-molecular density' methods (cf. of alcohol is 46 weight g., and that of glycerine 92 g. If 46 g. of alcohol and 92 g. of glycerine are each dissolved in 1,000 grams of water, the solutions freeze at the same temperature, viz., 1.89 C. We
(C 2
7

H 0)
6

ought to expect this, since the solutions contain equal numbers of molecules of the solute. If we add canesugar to 1,000 grams of water until the freezing1.89 C., we can get the point of the solution is
gram-molecular weight of cane-sugar.
It will take

128

MOLECULAR WEIGHTS.

about 342 grams, hence the molecular weight of In the case of urea cane-sugar is about 342. H 60 (CON 2 4 ), grams would be required;
of grape-sugar, 180 grams; hence the molecular weights of these substances are 60 and 180, respectively.
In practice, much smaller amounts of solute and solvent are used, but the principle is as The apparatus for molecular weight stated. determinations by the freezing-point method is shown in Fig. 36. It consists essentially of a
delicate thermometer,

reading to ToVoth of a

degree,

and a thin

glass tube to hold the solvent.

The jar surrounding the tube contains a suitable This is stirred by the wire freezing mixture. the stirrer. First, freezing-point of the pure
solvent
solute
is
is

obtained, then a weighed amount of added through the side-tube, and the

freezing-point of the solution is determined. The difference is the freezing-point depression. The formula for the calculation of the .molecular
FIG. 36.

weight

is,

Depression,
in

aqueous

solution,

1.89Xwt. of solute XI, OOP Mol. wt. of solute Xwt. of solvent


sol-

1.89

is

the gram-molecular depression for water; for other


it

vents

must be determined by means

of a solute of

known

molecular weight.

148. Boiling Point


its boiling,

Method.

Just as a solute retards the freezing of the solvent, so it retards Of course the i, e., it raises the boiling temperature.

OSMOTIC PRESSURE.
solute

129

volatile at the boiling temperature of the But, just as gram-molecular weights of cane-sugar, grape-sugar, urea, etc., each dissolved in 1,000 grams of water,

must not be

solvent.

give solutions having the same freezing-point, so they give solutions of the same boiling temperature. While water boils at 100
C., under 760 mm., a solution containing a gram-molecular weight of solute in 1,000 grams of water boils at 100.52 C. Hence, by adding a solute of unknown molecular weight to 1,000 grams of water at 760 mm., until the boiling-point of the

solution reaches 100.52

C.,

we can determine

its

gram-molecular

weight.

149.

Osmotic Pressure.

Under " hydrogen," 52, we learned that if a porous cup of air (Fig. 14) is immersed in hydrogen, this gas enters, the cup so much more rapidly than air can get out, that there is an increase of pressure inside the cup. Suppose the " " were a closed vessel made of pallacup " "

dium,
(cf.

metal which

53),

occludes hydrogen and through which hydrogen can

Assume pass while air cannot (Fig. 37). that the air inside was under one atmosphere
pressure.

pressure inside one atmosphere.

Hydrogen would enter until its was equal to that outside, viz.,

But, since the air originally in the palladium vessel had a pressure of one atmosphere, the total pressure inside would

now be two atmospheres.

If the vessel

com-

municated with a column of mercury, the height to which the mercury was raised would
indicate" the excess of pressure inside the palFIQ 37>

ladium
If

vessel.

we

sugar,

replace the palladium vessel of air by a water solution of and the surrounding hydrogen by pure water, we shall

130

MOLECULAR WEIGHTS.
for solutions.

have the corresponding phenomenon


osmosis.
the
"

We

call it

The sugar
"
of

solution
is

thistle

which

be in a thistle tube (Fig. 38), covered water-tight with parchment

may

paper.

An egg-shell, with a tube attached, may be used


membrane of the shell replaces The parchment and membrane are
i. e.,

instead; here the lining

the parchment.

semi-permeable,

they permit the water molecules

to pass freely, but not the sugar molecules (or only " " cell to make the a very little). Water enters the
result

The pressure of water inside equal that without. is to increase the volume of liquid inside, and
some
of
it

to force

up the

tube.

If

the

membrane

is

strong enough, and permits no sugar to pass outward, the column will rise until its hydrostatic pressure
cell as rapidly as it enters. condition of equilibrium is reached, the excess of inside pressure is the osmotic pressure of

causes water to leave the


this

When
FIG. 38.

For accurate work osmotic pressure cells strong earthenware into the pores of which cupric *ferrocyanide, Cu 2Fe(CN) 6 has been precipitated.
the solution.
are

made

of

Now,
urea,
etc.,

if

gram-molecular weights of cane-sugar, grape-sugar,

are dissolved in 1,000 grams of water, the osmotic pressures

of the solutions, like the boiling-point elevations

and

freezing-

point depressions, are equal. Osmotic pressure methods are not used much in getting molecular weights because the other

methods are easier to carry out. Just as gas pressure is pro40), so the osmotic pressure is portional to the density (cf. proportional to the concentration of the solution. Osmotic pressure
is

also proportional to the absolute temperature (Charles'

Law).

150.

Methods

of

Obtaining Exact

Molecular

Weights.
All the

weights;
analysis.

exact molecular weights are

methods described give only approximate molecular found by quantitative

EXERCISES.
The methods used may be

131

illustrated by the case of acetic the exact molecular weight of this substance may be found by a study of its silver salt, AgC 2 3 2 Silver acetate contains silver, carbon, hydrogen, and oxygen.
acid,

HC H
2

2;

The per cent

of the silver being found by analysis to be 64.65, that of the remainder of the molecule must be 35.35. The

atomic weight of
as exactly 16,
silver
is

silver, if we take the atomic weight of oxygen very nearly 107.94; the weight (x) of all of the acetate molecule except the silver is, therefore, found from

the equation,

Hence x = 59. 02.


Since acetic acid
is

silver acetate

with the

hydrogen, we must add

to 59.02 the

silver replaced by number representing the

weight of the hydrogen that 107.94 parts of silver replace. This Hence the exact molecular weight of acetic acid is is 1.008.
60.028.

151. Exercises.
1
.

If 1

volume

of

phosphorus vapor unites with 6 volumes of

chlorine to give 4 volumes of phosphorus trichloride, how many atoms, at least, are there in a molecule of phosphorus? 2. If, at the boiling point of sulphur, 1 c.c. of the vapor unites

with 8
the

c.c.

number

3. If

oxygen to give 8 c.c. of sulphur dioxide, calculate atoms in a molecule. 275 c.c. of a gas at 25 C. and 715 mm. weigh 0.46 gram,
of

of sulphur

calculate the molecular weight of the gas. 4. The molecular weight of a gas is 60.
of 290 c.c. of
5.
it

Calculate the weight

at 13

C. and 800

mm.

500

c.c. flask of air

740

mm. When

filled

weighed 40.495 grams at 18 C. and with ether vapor at 50 C. and 740 mm.

132
it

MOLECULAR WEIGHTS.

weighed 41.2605 grams. Calculate the weight of one liter vapor at 50 C. and 740 mm. Calculate the molecular weight of ether. 6. In a Victor Meyer vapor density apparatus 0.1387 gram of a compound expelled 47.2 c.c. of dry air at 24 C. and 735
of ether

mm. What is the molecular weight of the compound?

CHAPTER
152. Determination of

XIII.

ATOMIC WEIGHTS.
we were
Atomic Weights. As was to obliged postpone the

stated in

97,

determination of atomic weights until we had learned how the molecular weights are obtained. Now, since the common methods of getting molecular
143 to 145, apply only to weights, described in gases, the atomic weights of elements are determined
primarily from the molecular weights of the gaseous compounds of the elements. The tables will show

how

the

method works

for chlorine
in.

and carbon.
IV.

ii.

134

ATOMIC WEIGHTS.
chlorine

can all be vaporized and their molecular weights determined For con144). by vapor density methods (cf. have been made molecular the weights venience, In actual determinations the figures would be exact.

The

compounds

of

column

only approximate. The per cent of chlorine (column III) in each compound is found, with great accuracy, by quantitative chemical analysis. Multiplying the

numbers

of

column

hundredths, gives represent the weight of the atoms of chlorine in the molecule of the compound, or the grams of chlorine

by those of III, taken as These the figures of column IV.


II

The in the gram-molecular weight of the compound. smallest numbers in this column are approximately
35.5,

and the

35.5.

The atomic weight

larger ones almost exact multiples of of chlorine is, thus, ap-

proximately 35.5. In the case of carbon (see table) we can make an additional column (II) since the compounds named
in.
IV.
V.

ACCURACY OF THE METHOD,


are all gaseous under ordinary conditions. atomic weight is, apparently, about 12.

135

The

Definition of Atomic Weight.


to define atomic weight.

We are now ready


of

The atomic weight

an

element

is

the

number representing the smallest

weight of the element in the gram-molecular weight of any of its gaseous compounds.
153. Accuracy of the Method. of the atomic weights of chlorine

found from the tables of


of

152,

The correctness and of carbon, as depends upon the

the molecular weights. Since these accuracy cannot be determined with great exactness by the

methods used, the atomic weights derived from them


Exact atomic weights are are only approximate. obtained from the equivalent weights (cf. 97).

The equivalent weight

of chlorine

is

35.45.

Since

the approximate atomic weight and the equivalent weight are almost equal numerically, the accurate equivalent is taken as the atomic weight. In the case of carbon the equivalent weight, as obtained from the ratio of carbon to oxygen in carbon dioxide, is very nearly 3.003. As the atomic weight obtained from the table of 152 is about 12, the
exact atomic weight is obtained

equivalent weight

by

4.

weight of carbon 12.01. multiply the equivalent weight to get the atomic weight is the valence (cf. 132).

by multiplying the This makes the atomic The factor by which we

136

ATOMIC WEIGHTS.

Note that the atomic weight found from the molecular weights
is

of

the greatest atomic weight the element can have. The study new compounds of the element may make it necessary for

chemists to choose some smaller number, but not a larger one.

154.

Summary

of the

Method.

general method of selecting the atomic weights of such as hydrogen, nitrogen, bromine, iodine, sulphur, phosphorus, arsenic, and some others is as given for chlorine

The

elements

and carbon.
(1)

In each case we must have the following data: The molecular weights of several gaseous compounds

of

the element.
(2) The number of grams in the gram-molecular weight of each compound that represents the weight of the element itself. The smallest of these is the approximate atomic weight.

This is either (3) The equivalent weight of the element. numerically equal to the atomic weight, or must be multiplied by some small integer to give it.

Substances differ 155. Dulong and Pe tit's Rule. greatly in their capacity for heat, that is, in the

amount

of heat acquired (or lost)

by them when they

are heated (or cooled) through a given range of temThis varying heat capacity, or specific perature.
heat,
of different

substances

is

measured by the

cf. 55) a given can substances impart to a given weight weight of another substance, such as water. If we heat two 100 g. balls, one of iron and one of lead, to

number

of units of heat (calories,

of the

the same temperature, say 200

C.,

and plunge them


C., the

into equal weights of water at 20

water

will

DULONG AND PETITS RULE.

137

be heated to a higher temperature by the iron ball than by the one of lead. The specific heat of iron is greater than that of lead. Water has a greater heat capacity than any other substance except hydrogen
(cf.

71).

In 1819, Dulong and Petit observed the existence of the rule which is called by their names; the rule

may be stated as follows :

The

specific heat of
is

a solid element multiplied by

its

atomic weight

a constant (about 6.25). trations appear in the following table: -

Some

illus-

ELEMENT.

138
its

ATOMIC WEIGHTS.

for

approximate atomic weight. x in the equation,


6.25 ,=x. 0.0567

We

simply solve

Hence #=110.

The

exact atomic weight of

cadmium

is

about 112.

156. Application of

Atomic Weight Methods.

atomic weight of be illustrated by the case of zinc. The method used for chlorine will not apply here; we must, therefore, study the action of zinc with elements of known atomic weight, e. g., with hydrogen, chlorine, and oxygen.
in actually getting the

The methods used

an element

may

When zinc is dissolved in certain dilute acids, it sets free hydrowe can thus get the equivalent of the zinc. Now, if for each atom of zinc dissolved an atom of hydrogen is set free, the
gen;

gram-atomic weight of zinc must equal


i.

its

equivalent weight,

e.,

32.7 grams.

A second element with which we can compare zinc is chlorine. The compound of these two elements, zinc chloride, may be made either (1) by dissolving zinc in hydrochloric acid and
evaporating the solution, or
(2)

by burning

zinc in chlorine.

The
by

relation of zinc to chlorine in zinc chloride, as determined quantitative analysis, is about as 32.7 35.5. Hence, if
:

chlorine

and

weight of Let us, however, consider a third compound of zinc, viz., its oxide. This substance may be made by heating zinc in oxygen,
or, better,

have united atom for atom, and the atomic chlorine is 35.5, the atomic weight of zinc must be 32.7.
zinc

by

dissolving zinc in dilute nitric acid

and heating the


proportions

zinc nitrate

formed to a high temperature.


also,

The
zinc

of the elements in zinc oxide are,

zinc, 65.4 parts, to

oxygen,

16 parts.

Here,

we might assume that

and the other

ATOMIC WEIGHT METHODS.


element are united atom for atom;
zinc
is
if

139

so,

the atomic weight of


together:
re-

65.4-

To compare
'(1)

these results let us write


of

them down
(1

One gram-atomic weight placed by 32.7 grams of zinc. (2) One gram-atomic weight
with 32.7 grams of zinc.

hydrogen

gram) was

of chlorine (35.5 grams) united

(3) One gram-atomic weight of oxygen (16 grams) united with 65.4 grams of zinc. Evidently we cannot assume that one atom of zinc unites with

one atom of the other element in each of the three cases; for we cannot have some zinc atoms with a weight of 32.7 each, and
zinc

others with a weight twice as great. If the atomic weight of is 32.7, one atom of oxygen must unite with two atoms of
zinc to
is

form zinc oxide; if, however, the atomic weight of zinc atoms of hydrogen must have been replaced by one of zinc, and two atoms of chlorine must have united with one
65.4, two

of zinc.

The molecular weight of zinc chloride, or of zinc oxide, would help us; that of zinc chloride is the one used; for the weight of a known volume of its vapor has been obtained. By a solution
of the equation,

Wt.

of 1

1.

zinc chloride vapor


of
1
1.

Wt.

oxygen

Mol. wt. of zinc chloride Mol. wt. of oxygen

the molecular weight of zinc chloride was found in an actual experiment to be about 134. This result is sufficiently accurate
to enable us to decide that the molecular weight of zinc chloride is 136.4 rather than one-half or twice this number.

molecule of zinc chloride thus contains 65.4 parts of zinc

and 71 parts (two atoms) of chlorine. We do not, however, know whether the two atoms of chlorine are united with one atom of zinc having a weight of 65.4, or with two, each having a
weight of 32.7;
or with three, each having a weight of 21.8, etc.

140

ATOMIC WEIGHTS.
apply Dulong and Petit's rule. By substituting the heat of zinc, found by experiment (0.094), in the ex-

We now
specific

pression,

6.25
r^

specific

heat

= atomic

weight,

we

shows us that the number 65.4


sub-multiple of
it.

obtain 66.5 for the approximate atomic weight of zinc. This is to be taken rather than any

157. Exercises.

Use the following data to calculate the approximate atomic weight of nitrogen. If the equivalent weight is 4.67, what is the exact atomic weight?
1
.

WEIGHT OF

LITER, IN GRAMS.
1.256
1.34
1.97-

PER CENT OF NITROGEN.


100.

Nitrogen,
Nitric oxide,

46.67
63.64

Nitrous oxide,

Ammonia,
2.

0.762

82.35

From

the following data calculate the atomic weight of

hydrogen.

How is the exact atomic weight obtained?


1

WEIGHT OF

LITER, IN GRAMS.
chloride, 1.61

PER CENT OF HYDROGEN.


2.74
1.23

Hydrogen

IJydrogen bromide, 3.61 0.09 Hydrogen,

100.00
5.88
17.65

Hydrogen sulphide, 1.542 0.762 Ammonia, 0.717 Marsh gas,

25.00

EXERCISES.
3.

141
if

What
The

is

its specific

heat

the atomic weight (approximate) of an element If it is 0.0952? is 0.033?

4.

specific

heat of arsenic

is

0.0814,

times as heavy as oxygen. molecule?


5.

How many

and its vapor is 9.37 atoms are there in its

Dulong and

Calculate the specific heats of the following elements from Petit's Rule: gold, nickel, potassium, lead, zinc.

fC

CHAPTER
ACIDS, BASES,
158. Acids.

XIV.
SALTS.

AND

we

shall

In all of our study of Chemistry have to deal constantly with bodies belongfirst

ing to the classes acids, bases, or salts. Let us consider some of the acids. One of these,
hydrochloric acid,

viz.,

we have

already studied at some

length;

other important acids are nitric acid, sul-

phuric acid, acetic acid, and tartaric acid. short description of these will be given here.

Only a

Nitric acid, is a colorless liquid. It ordinarily has a 3 sharp odor and is very corrosive in concentrated form. It turns the skin yellow. A dilute solution of nitric acid is sour, turns blue litmus and neutral litmus pink, decomposes carbonates,
,

HNO

e. g.,

marble, or calcium carbonate, and acts upon many metals. is a heavy, oily liquid which dissolves 2 S0 4 Sulphuric acid,

much heat. It chars organic substances, and, therefore, becomes dark colored when exposed for a time to the dust of the air. Its dilute solution has a sour
in water with the evolution of
taste,

and acts upon litmus and carbonates as

nitric

and hydro-

chloric acids do.

With many metals


2
3

dilute sulphuric acid gives

sulphates and hydrogen.


Acetic acid,

HC H

2,

is

colorless,

sharp-smelling liquid.

has a sour taste, acts upon litmus, and decomposes carbonates. Vinegar is a dilute solution of acetic acid. Tartaric acid, 2 C4H 4 06, is a white, crystalline solid, soluble
Like the other acids,
it

in water.
acids.

Its solution

has properties similar to those of the other


142

BASES.
All of the acids

143
acid,

named, except hydrochloric

may be looked upon as water joined to an oxide. The oxide is called the anhydride of the acid.
Thus nitrogen pentoxide,
acid, for

5,

is

the anhydride of nitric

N
acid.

+H

HN0

3.

Similarly, sulphur trioxide, SOs,

is

the anhydride of sulphuric

The most important property


power

of all acids

is

their

When

of reacting with the hydroxides of metals. a solution of any of the above acids is treated

with a solution of a metal hydroxide, e. g., sodium hydroxide, an evolution of heat takes place, and if the correct amount of sodium hydroxide is used, the
taste of

the acid,

its

power

to

change litmus, and to

act

upon
acid

carbonates

and

metals, will all disappear.

The

has

been neutralized

by the sodium

hydroxide.

159. Bases.

--The

hydroxide and its 74). given (cf.


Sodium
hydroxide,

general properties of sodium relation to water have already been

NaOH,

is

a white solid which attracts


air,

moisture and carbon dioxide from the

and thus becomes

converted into sodium carbonate.

and neutral litmus


bitter,

to blue, feels

changes pink soapy to the touch, and has a


resembles

Its solution

alkaline taste.

Potassium

hydroxide,

KOH,

sodium hydroxide

144
closely.

ACIDS, BASES,

AND

SALTS.

Its aqueous solution has properties almost identical with those of sodium hydroxide. Ammonium hydroxide, 4 OH, is not known in the free con-

NH

aqueous solution smells strongly of ammonia, owing to the constant evolution of this gas, but its reaction to litmus, etc., is much like that of sodium and potassium hydroxides.
dition.
Its

Calcium hydroxide, Ca(OH) 2 is a white solid made by adding Calcium the necessary amount of water to quicklime, CaO. hydroxide is slightly soluble in water; the solution is called
,

lime-water.

Barium hydroxide, Ba(OH) 2 cium hydroxide. Its solution is


,

is

much more

soluble than cal-

called baryta water.

hydroxides, and many more, are grouped together under the general name, bases. The most active bases are sodium and potassium
All
of

these

hydroxides, which, with


called alkalies.

ammonium

hydroxide, are

As has already been


upon

stated

(cf.

75), hydroxides

may be looked

as water with half of its hydrogen replaced by a metallic element. This is true of calcium hydroxide, having the formula

O1T

no

less

than of sodium hydroxide,

NaOH.
of as derived

OTT

The formula CaQjj, however, must be thought


from 2 HoO, or -H
fTT

OTT

OH
Similarly,

X5-

the

formula

FeOH

or

OH
-<

Fe(OH) 3

for ferric hydroxide,

is

derived from

(HOH HOH (HOH

by

re-

placing half of the hydrogen there represented

by Fe.

TWO CLASSES OF OXIDES.


1 60.

145
the formuthey all

Neutralization.

A comparison of
will

las of the

hydroxides named

show that

contain the group (called hydroxyl) taken one or more times. On the other hand, the formulas of

OH

the acids

show that

the acids all contain hydrogen,

taken once, twice, etc., in each formula. Furthermore, the neutralization of acids by bases produces salts and water, as is shown by the following equations
:

NaOH+HCl KOH+HC1'
2

NaCl+H O.
2 2
.

KC1+H 0. K S0 +2 H 0. 2 KOH+H S0 2 NH OH+H S0 (NH S0 +2 H O. NH OH+HN0 NH N0 +H 0.


4
2

4) 2
3

Ca(OH) 2 +H 2 S0 4 Ba(OH) 2 +2 HC1

>

CaS0 4 +2
BaCl 2 +2

H 0. H O.
2

The neutralization of properties which takes place when a basic hydroxide and an acid are brought together thus consists in the union of the hydrogen of the acid with the hydroxyl of the base to form water. The
metal of the hydroxide and all but the hydrogen of the acid are found, on evaporation of the water, combined in the resulting salt.

The formula
hydrogen
161.
is

of

an acid minus the replaceable


(cf.

called the acid radical

105).

learned

We have already metals and non-metals 8 and that (cf. 72) differ decidedly both in physical and in chemical
Two
Classes of Oxides.

properties.

Both unite with oxygen, giving oxides,

146

ACIDS, BASES,

AND

SALTS.
rise to

but the two classes of oxides give


mentally different classes of
acids.

two fundasubstances, bases and

The oxides of metals, such as unite with water to produce bases :

CaO and Na20,


2.

CaO+H O
2

->

Ca(OH)
2

Na,0+H
acids

NaOH.
give

The oxides of non-metals, on the other hand, when they unite with water: -

S0

C0
P
The
2

+H +H
5

2 2

+3 H O

H SO H C0 > 2 H PO
2

3.

3. 3

4.

oxides of non-metals are thus the anhydrides the oxides of metals are of oxygen acids (cf. 168)
;

the anhydrides of basic hydroxides.


162. Action of

Oxides with Acids and Bases.

Oxides of metals react with acid anhydrides to give salts, or with acids to give salts and water.

+C0 MgO+2 HC1


CaO
If
2

CaC0

3. 2

MgCl 2 +H

0.

water

is

of oxide

and water, and

present, the equations ought to show, (1) the union (2) the action of hydroxide and acid:
2

CaO+H
Also,
2

Ca(OH) 2
2
2 4

Ca(OH) 2 +2 HCl

CaCl 2 +2

H 0.
2

Na 0+H
2

NaOH+H S0

NaOH; Na S0 4 +2
2

H 0.
2

ACID SALTS.
When the
(1)
(2)

147
write:

gas carbon dioxide acts

upon lime-water, we
3
;

C0

+H

H CO
2

Ca(OH) 2 +H 2C0 3
Salts

CaC0

+2 H 0.
2

163. Salts.

may

be looked upon as acids

in which hydrogen has been replaced by metals. By no means all of the hydrogen of many acids is re-

metals, but when all that can be has been replaced, the resulting substance is called a

placeable

by

normal

The normal salts formed by such strong salt. acids as sulphuric acid, nitric acid, and hydrochloric acid with such electro-positive metals as sodium,
potassium, and the group
in their properties,
i. e.,

ammonium,

are neutral

they will not turn blue litmus nor but will red, blue, produce in sensitive litmus red, a characteristic lavender color. The taste of such
salts

resembles that of

common salt.

But a salt may be normal without being neutral. Thus, sodium carbonate is a normal salt, but the reaction of its solution
toward litmus
is

that of a base.

Ferric sulphate solution,

on

the contrary, has an acid reaction.

164. Acid Salts.


of the acid
is

In

many

cases, the

hydrogen

stages
salts

(cf.

replaceable by metals in two or more 126) hence, there may be two or more
;

formed by

the acid with the

same

basic hydroxide.
:

The

following equations illustrate this

NaOH4-H S0
2

4 4

NaOH+H S0
2 2

NaHS0 +H 0. Na S0 +2 H O.
4 2
2

KOH+H C0 2 KOH+H C0
3 2

KHC0 +H 0. K C0 +2 H 0,
3
2

148

ACIDS, BASES,

AND

SALTS.

while
is

The substance NaHSCX is sodium hydrogen sulphate, Na2S0 4 is sodium sulphate. Similarly, KHCO 3
potassium hydrogen carbonate, but
carbonate.

K C0
2

is

potas-

sium

salts in which there is still replaceable hydroare called acid salts. Acid salts may usually be gen converted into normal salts by the addition of enough

The

of the hydroxide to replace all the replaceable hydrogen, and, conversely, normal salts may be converted

into acid salts

by treatment with
4

free acid.
2 2

Thus :

So, also,

NaHS0 +NaOH NaHCOs+NaOH Na S0 -fH S0 4 Na C0 +H C0


2 2

Na S0 4 +H 0, and Na C0 3 +H 20.
2

2 2

NaHS0 NaHC0

4,

and

3.

Solutions of acid salts have usually an acid reaction toward litmus, but not always; for the reaction may
alkaline, as in the case of sodium hyand disodium hydrogen phosphate, carbonate drogen

sometimes be

Na HP0
2

4.

A salt may be considered from 165. Basic Salts. two points of view, either (1) as an acid, the hydrogen of which has been replaced by a metal, or (2) as a
hydroxide with
its

hydroxyl (OH) replaced by a non-

metallic element or

by an

acid radical

(cf.

160).

NaCl, may be looked upon as hydrochloric acid, HC1, with hydrogen replaced by sodium, or as sodium hydroxide, NaOH, with hychloride,

Thus sodium

droxyl

replaced

by

chlorine.

Similarly,

calcium

BASICITY
,

AND

ACIDITY.

149
,

is calcium hydroxide, chloride, CaCl 2 Ca(OH) 2 with hydroxyl replaced by chlorine; and calcium sulphate, CaS0 4 is calcium hydroxide with hydroxyl
,

replaced

by the acid

radical

S0 4

Now,

just as in

2 SO4, the hydrogen may be replaced sulphuric acid, half at a time, so in calcium hydroxide the hydroxyl

groups
stages.

may

be

substituted,

theoretically,

in

two

We might, therefore, have from calcium hydroxide and hydrochloric acid two compounds,
OTT
(1)
r^i
,

CaQ
still

and

(2)

CaQ.

Just as

we

call

salt

which
salt,

contains replaceable hydrogen an acid


call
salt.
:

so

we

one having replaceable hydroxyl

groups a basic

To
2

illustrate

Just as phosphoric acid,


salts, viz.,

have two acid sodium

H PO may NaH P0 and


3 4,

Na HPO
have two

4,

so

bismuth

hydroxide,

Bi(OH) 3

might
OTT

basic nitrates, viz..

Bi

The normal nitrate is,


It
is

of course,

Bi(NO 3 ) 3

ently, a

to be noted, however, that some basic salts have, apparmore complex constitution.

1 66.

in

The number of stages Basicity and Acidity. which the replaceable hydrogen of an acid can be
by metals determines the
acetic
acid,

substituted
acid.

basicity of the
nitric

Thus, hydrochloric acid, HC1,


3,

acid,

HNO

and

HC H O
2

2,

are monobasic

150
acids;

ACIDS, BASES,

AND
,

SALTS.
acid,
3 4,

H S0
2

4,

and sulphuric carbonic acid, 2 CO 3 are dibasic; while phosphoric acid,

H P0

is tribasic.

In the same way, the number of stages in which the hydroxyl groups of a basic hydroxide might be replaced by acid radicals

by non-metals determines, roughly, the acidity of the hydroxThus sodium hydroxide and potassium hydroxide are monacidic bases; calcium hydroxide, Ca(OH) 2 and barium
or
ide.
,

hydroxide,

Ba(OH) 2

are diacidic;

while bismuth hydroxide,

Bi(OH) 3

is triacidic.

167. Equivalent Solutions of Acids, Bases,


Salts.
Solutions are often

and

made of such a " strength," or concentrathat tion, they contain one gram-molecular weight of Such solutions are solute in each liter of solution.
called gram-molecular, or molar, solutions. Thus, 36.5 grams of hydrogen chloride (HC1), 98 grams of sulphuric acid (H 2 S0 4 ), 58.5 grams of common salt (NaCl), or 40 grams of sodium hydroxide (NaOH),

each in a
1 c.c. of 1 c.c. of

liter of their solutions,

form molar solutions; _l


will just neutralize

a molar solution of

NaOH

a molar solution of HC1, and will form 0.001

of a
will
1

take 2
of

molar weight of NaCl, i. e., .0585 gram. But it c.c. of molar NaOH solution to neutralize molar molar

c.c.

c.c. of

hydroxide,
j[

H 2S0 4 Obviously, it will also take HC1 to neutralize 1 c.c. of molar barium In order to have solutions of Ba(OH) 2
. .

TT^
II

such concentration that they will react, cubic centimeter for cubic centimeter, chemists use normal
solutions.
!

normal solution

of

an acid contains

FIG

39.

per liter; lent weight of metal per

hydrogen (an equivalent weight) gram normal solutions of bases and salts contain an equivaliter.

of replaceable

Thus, normal solutions of

NaOH,

NOMENCLATURE OF

ACIDS.

151

HC1, and NaCl have the same concentrations as molar solutions'' but a normal solution of H 2 S0 4 contains 49 grams (98-5-2) of solute per liter, and one of Ba(OH) 2 85.5
of these substances;
,

g.

of solute per liter.

Decinormal

I
I

N\
0.1

N, or

),

half-normal

/N
I

TT,

or 0.5

\
)

etc., solutions

are often used.

Nomenclature of Acids. Acids consisting two elements are called binary acids. They are Thus designated by the names of both elements. HBr is hydrobromic acid, and H2 S is hydrosulphuric
1 68.

of

acid.

The anhydrous compounds are named


of

like

ordinary compounds

two elements

(cf.

110);

thus: hydrogen chloride, hydrogen

sulphide, etc.

such acids are called chlorides, broThus, the sodium salt of sulphides, etc. sodium is called acid iodide, and the barium hydriodic salt of hydrochloric acid is barium chloride.
salts of

The

mides,

Most

acids,

however, are ternary,

i. e.,

consist of

three elements:

ment, which is These are given the name of the third acid, etc. element with the final syllable ic. This method of nomenclature applies, however, only to inorganic
acids; organic acids, e. g., acetic, tartaric, citric, picric, etc., acids are quite arbitrarily named. When there are two acids containing the same

Hydrogen, oxygen, and a third eleusually a non-metal. Such are nitric

three elements in different proportions, the ending

152

ACIDS, BASES,

AND

SALTS.

of the acid containing the smaller proportion of the oxygen is made ous, while the ending of the one conof this element is made ic. Thus, forms with hydrogen and oxygen at least nitrogen two compounds which are acids; of these the one its formula is HN0 2 containing the less oxygen is called nitrous acid, while the one containing the larger proportion of oxygen is called nitric acid. So sulphur forms with hydrogen and oxygen both

taining

more

sulphurous acid,

H S0
2

3,

and sulphuric
chlorine,

acid,

H S0
2

4.

The

acids formed

by the element

the best illustrations of nomenclature.

however, give Chlorine forms with

hydrogen and oxygen four acid compounds, the compositions of which are represented by the formulas:

HC10 HC10 HC10 4


The second
of these
3,
.

k^

compounds,

HC10

2,

is

called chlorous acid

the third, chloric acid; the first, because it contains less oxygen than chlorous acid, is called hypochlorous acid (" hypo " signifies " " " under or lower than "); the fourth, because it has more

oxygen than chloric

acid, is called perchloric acid.

Ternary acids containing oxygen are


oxygen acids, or oxy-acids.

also called

The salt of an 169. Nomenclature of Salts. acid ending in ous is given the ending ite, the prefix
hypo remaining unaltered,
if

present.

NOMENCLATURE OF
Thus, sodium
salt of nitrous acid is

BASES.
sodium
nitrite,

153

the potassium salt of chlorous acid is potassium chlorite, KC10 2 and the calcium salt of hypochlorous acid is calcium hypochlorite,

Ca(OCl) 2

The

salt of

an acid ending

ate, the prefix per

in ic is given the suffix remaining unchanged, if present.


of nitric acid
is is

Thus, the

ammonium salt

ammonium
chlorate,

nitrate;

the barium salt of chloric acid

barium
is

Ba(C103)2;

the potassium salt of permanganic acid


ate,

potassium permangan-

KMn0

4.

In many cases there are two salts of the same metal with a given acid, as, for example, two iron sulphates, designated by the formulas FeSO 4 and

Fe2(SO 4 )3, respectively. To distinguish between these the ending of the name of the metal is changed to ous in the sulphate in which the metal has the lower valence and to ic in the case in which the metal has the higher valence.
Thus, FeS0 4 is called ferrous sulphate, just as FeCl 2 is called 111); and Fe2(S04)s is called ferric sulphate, ferrous chloride (cf. just as FeCl 3 is called ferric chloride.
,

The name of a 170. Nomenclature of Bases. basic hydroxide contains the names of all the elements
of

which the hydroxide

is

composed.

The ending

is

being treated as an element. ide, the radical When there are two basic compounds of hydroxyl with the same metal, the metal ends in ous in the

OH

hydroxide in which it has the lower valence, and in ic in the hydroxide in which it has the higher valence.

154
Thus,
ferric

ACIDS, BASES,

AND

SALTS.

hydroxide,

we have cuprous Cu(OH) 2 also hydroxide, Fe(OH) 3


; .

hydroxide,

Cu 2 (OH)

2,

ferrous

hydroxide,

Fe(OH) 2

and cupric and


,

171. Exercises.
formed when a solution of sodium hydroxide is nitric acid? Barium hydroxide by sulphuric acid? Ammonium hydroxide by acetic acid? 2. Name the calcium salt of carbonic acid; the lead salt of
1.
is

What

neutralized

by

hydrochloric acid
salt of

hypochlorous acid;

the potassium salt of chloric acid the barium the sodium salt of chromic acid;
;

the silver salt of hyponitrous acid. 3. 8 grams of sodium hydroxide are contained in 50

c.c.

of

a solution; how many grams would this be in every liter? 4. 112 grams of potassium hydroxide are required to neutralize all the hydrochloric acid in a solution; how much of the
acid

was there?

If

the solution were evaporated, what salt would

be found?
5.

How many grams of it?


is

What

the formula of the acid salt formed by sodium

hydroxide and sulphurous acid? Its name? 6. 49 grams of sulphuric acid were required to redden litmus
in a solution of

potassium hydroxide;

was there
formed?
7.

in solution?

How much

how much hydroxide potassium sulphate was

What are

the formulas of the basic chlorides theoretically

possible from a consideration of the formula Bi(OH) 3 ? 8. How many grams of solute to the liter are there in normal solutions of the following: KC1, BaCl 2 2 H 2 0, AgN0 3 H 3 P0 4 A1 2 (S0 4 ) 3 NH 4 C1, Na 2C0 3 ? 9. It takes 6.3 c.c. of normal sodium hydroxide to neutralize the sulphuric acid in 20 c.c. of a certain solution. How much sulphuric acid is present? Give its concentration in terms of a normal solution.
. ,

CHAPTER XV.
IONIZATION.

Double Decomposition of Acids, Bases, and By far the most common reactions that take place in solution are those of double decom172.
Salts.

position

(cf.

92)

The essential thing about a double

decomposition is that the two reacting substances behave as though they were broken up into two
kinds of parts: An acid into hydrogen and an acid radical; a base, into hydroxyl and a metal; a salt, into a metal and an acid radical. The reaction consists in

the exchange of these parts.

Illustrations

are:

tf*^) NaOH+HCl (2) NaOH+NH Cl


4

(3) (4)

BaC0 +H S0 AgN0 +KCl


3 2 3

NaCl+H 0; NaCl+NH OH T BaS0 1 +H C0 T


2

>

AgCl

+KN0

3.

The double decomposition reactions of acids, bases, and salts, together with the physical properties of their solutions, have given rise to a theory that they
are actually dissociated in solution
173.
(cf.

175).

In
of

The Freezing Points, Etc., of Solutions. 147 we learned that if gram-molecular weights
'

two substances,

e.g., glycerine
155

and

alcohol, are

156

ION I Z ATION.

each dissolved in 1,000 grams of water, the freezing 1.89 C. points of the solutions are the same, viz. This does not apply to acids, bases, and salts. The
:

freezing-point depression for chloride in 1,000 g. of water

58.5

g.

of

more.

is not 1.89 In dilute solution the degression is practically twice what we should expect. If the freezing point

sodium C., but

depression depends on the concentration of the molecules present, then the molecule of sodium chloride must be dissociated into two particles, each

molecule in lowering the freezing point. study of the boiling point and of the osmotic pressure of salt solution leads to the same
of
like a

which acts

conclusion.
eral, like

Acids, bases,
salt.

and

salts

behave, in gen-

common

174. Electric
acid, the

Conductance

of Solutions.

If

an

electric current is

passed through dilute sulphuric


61).

water

is electrolyzed (cf.

Pure water

does not conduct the current.

Water containing
conducts as well
if

HC1, NaCl,
as dilute

NaOH,

KNO
acid.

3,

etc.,

water contains glycerine, sugar, etc., it does not conduct readily. In electric conductance, then, as in double decomsulphuric
position, the rule
is

But

that acids, bases, and salts are

A solution active, while other substances are not. that conducts is called an electrolyte; one that does
not,

a non-electrolyte.

Solutions of acids, bases,

and

salts are not electrolytes for all solvents;

hydrogen

DISSOCIATION IN SOLUTION.
chloride dissolved in toluene
electrolyte.
(cf.

157

524) forms a non-

175.

Theory
of

of

Dissociation in Solution.

Be-

peculiar behavior of electrolytes, Arrhenius developed the modern theory of solutions

cause

the

(1887). in water,

He

considered that

when

salt is dissolved

it is

separated into particles, called ions. NaCl Na+Cl.


called

The

solute

is

an ionogen,

i.

e.,

ion-producer.

In the electrolysis of salt solution, the sodium goes to the kathode (electrode, cf. 61); hence it is

assumed that sodium ions carry + charges. The ions of chlorine, which go to the anode, are negatively
charged.
of salt
is,

The

ionic

equation for the dissociation


i

therefore,

>

NaCl

Na+Cl.

But while
ionized, the

two kinds

'Water permits (or causes) the salt to be of ions, since they have

charges, respectively, reunite to form molecular salt. Hence dissociation and recombination

and

balance each other

(cf.
7

73 and 244).

NaCl

Na+Cl.

For the dissociation of hydrochloric acid, sodium hydroxide, and sodium sulphate the equations are,
HC1
7

H+C1, and

NaOH 7
Na2SO 4
7

Na+OH;
2

Na+S0

4.

158

1ONIZATION.
total

The
total of

number of charges carried by the ion is equal to its valence as an atom or radical (cf. 135). Hydrogen and metals form + ions, or kations; non-metals, acid radicals, and hydroxyl form ions, or anions.
the

number of charges, and

charges

is

equal to the

Relation of Ions to

Atoms and Molecules.


all

The

ions are

not atoms; neither have they


etc., of solutions.

the properties of molecules.

They

act like molecules, however, in their effect on the freezing point,


If we ask why sodium in the ionic form is supin remain water without reacting with the water (cf. 74), to posed the answer is, that the sodium atoms (or molecules) are not free,

but carry very large electric charges, which completely change their behavior. So, yellow phosphorus, because it possesses more
energy, has properties different from those of the red form (cf. 345). When the charges on the ions of sodium are neutralized,

they become ordinary sodium, and at once react with water.

176. Explanation

of

Neutralization.

very

simple explanation of the properties of acids, bases, and salts, and of neutralization, follows from the
ionization
All acids in aqueous solution theory. in the same affect litmus way because they all give

hydrogen ions (H).

The turning

of

litmus red

is

simply an indication

of the presence of these ions.

Similarly, bases are substances

whose solutions conunion

tain hydroxyl (OH) ions. Neutralization is thus

essentially
to

the

of

hydrogen and hydroxyl ions


molecules of water.

form undissociated

DEGREE OF ION IZATION,

159

The

ionic equation for the neutralization of

sodium

hydroxide by

hydrochloric acid

is,

Na+OH+H+Cl

Na+CL+H 0.
2

When the water is removed, the sodium and chlorine


ions unite to give molecular sodium chloride.

The ionic view 177. Heat of Neutralization. of neutralization is supported by the fact that the
amounts of heat
evolved

when normal

solutions

(cf.

167) of the strong acids are neutralized by a given base, such as sodium hydroxide, are equal, namely,

13,700 calories. The same amount of heat is given when other strong bases, such as potassium and calcium hydroxides, are used. The ionic equations
off

showing

this are

K+OH+H+NOs
Na+OH+H+Cl
2

K+N~0

+H 0+13,700 cal.
2
2

Na+Cl+H O+ 13,700
4

cal.

Na+2 OH+2 H+S0

Na+S0 +2 H 0+27,400
4

cal.

Ca+2 OH+2 H+2 Cl

>

Ca+2 Cl+2 H 0+27,400 cal.


2

The equations show

that the heat of neutralization

is simply the heat evolved by the union of 1 g. of with 17 g. of ionic OH to form 18 g. of water. ionic

178.
Since

Degree
it is

of lonization.

the solvent that causes dissociation, dilute solutions This should be better conductors than concentrated ones.

160
is

ION I Z ATION.
From measurements of the conductivity of sulphuric has been calculated that the concentrated acid is only 0.7%
i. e. }

the case.
it

acid

ionized,

solution of the acid

only 7 molecules in every 1,000, while a normal is 51% ionized. Similarly, concentrated

(62%) nitric acid is only 9.6% ionized, but the normal solution, 82%. The increase in the ionization of strong acids, strong bases, and salts with increasing dilution finally stops, hence we conclude that at great dilutions the separation of the molecules into is complete. The acids and bases that are highly ionized at ordinary concentrations are chemically active; hence they " " " " are called acids and bases. must not be strong Strong
ions

confused with

"

concentrated
is

"
(cf.

79).

The degree

of ioniza:

tion for several substances

given in the following table

SUBSTANCE.

REPLACEMENT.

161

is

with silver nitrate solution, and that the precipitate not affected by dilute nitric acid. We use the silver

nitrate for its silver ions; these unite with chlorine ions to give silver chloride, which is insoluble.

Ag+NOa+Na+Cl
If,

AgCl

+Na+N0

3.

however, we add

silver nitrate solution to


,

dilute solution of a chlorate, e. g., NaClO 3 get a precipitate of silver chloride, because

we do not
no chlorine

ions are present.


is

The
.

chlorine of

sodium chlorate
which might
soluble.

part of the ion CIO S

Silver chlorate,

be

formed,

is

not

precipitated

because

Hence no

result is apparent.
*
(

Ag+NOa+Na+ClOs
Another
illustration:

Ag+N0 +Na+cib
3
,

3.

Ferrous
) 2 S,

ammonium

sulphide

(NH4

phide, FeS; but ammonium iron of potassium ferrocyanide solution, ions are not present.

chloride, FeCl 2 gives with a black precipitate of ferrous sulsulphide does not precipitate the

K4Fe(CN) 6

because iron

K4Fe(CN) 6 ;zi

K+Fe(CN)

6.

180.

Replacement;

the Electromotive Series. -

When

metals react with acids and with water to 57 and 74), the reactions produce hydrogen (cf.
are cases of replacement
(cf. >

92)
2

Zn+2 HC1

Na+H

ZnCl +2 H T NaOH+H T
.

162

ION I Z AT ION.
the ionic point of view, these equations are,

From

Zn+2 H+2

Cl
>

Zn+2 Cl+2 H T

Na+H+OH
in the transfer of the

Na+0~H+H T

According to the equations, the reactions consist charges of the ionic hydrogen to the metals. Some metals, e. g., silver, cannot

charges to hydrogen in this way, hence they do not react with acids to liberate hydrogen. A metal may replace, not only ionic hydrotheir

transfer

gen, but the ions of another metal

Zn+Sn+2

Cl
4

Zn+2 Cl+Sn i

Sn+Cu+S0

Sn+s64 +Cul
3

Cu+Hg+2 N0
a

>

Cu+2 N0 +Hg |
3

The metals and hydrogen may thus be placed

in

series, called the electromotive series (cf. Appendix x), in which the metals coming first replace those that succeed them, from the solutions of their salts.

One non-metal may also replace another 319 and 325) by the transfer of charges:
Na+B~r+Cl
2

(cf.

Na+Cl+Br.
2

H+S+2 I

H+2 I+S I

181. Oxidation

and Reduction

of Ions.

In

138

we

learned that an element

may

have

different

OXIDATION AND REDUCTION.

163

valences in different series of compounds. Thus, is bivalent in ferrous compounds, such as FeO, FeCl 2 and FeSO 4 but trivalent in the ferric comiron
,

pounds, Fe 2 O 3 FeCl 3 and Fe 2 (SO 4 )3.


,

is

bivalent in
2

MnO
.

Mn0
is

and MnCl 4
oxidize
it

So manganese and MnCl 2 and quadrivalent in Now, to change FeO to Fe 2 O 3


,
, ;

oxidation is possible be25) cause iron can increase its valence from 2 to 3. On
to
(cf.

the other hand, Fe 2 O 3 can be reduced to FeO because the valence of iron can fall from 3 to 2. For
exactly the same reasons that apply to the oxides, ferrous chloride is said to be oxidized when changed
to ferric chloride,

and

ferric chloride is said to

be

reduced to ferrous chloride, even though it is chlorine, and not oxygen, that is added or taken away. The
test applied is that in oxidation the valence is increased, while in reduction it is decreased. In the following oxidation equations valence symbols (cf. 133) are

used :

Fe'W+Cl'
2 Fe II (S04) II

+H
I

Feels'.
(S0 4 )
II

+O n

Fe 2 1II (S04) 3 II -hH 2

ir
.

We

carried

have seen (qf. 175) that the number of charges by an atom (or radical) acting as an ion
,

Accordingly, we may corresponds to the valence. represent the oxidation of FeCl 2 to FeCl 3 in solution,

by

the ionic equation, Fe

+2C1+C1

>Fe

+3

Cl.

164

ION I Z AT ION.

From

Fe" to Fe

the ionic point of view the oxidation of m consists in the taking up of an additional the ferrous ion. The iron is oxidized, charge by
ionic,
i. e., it

because the chlorine becomes


negative charge.

assumes a

For the reduction


the ionic equation
Fe
is:

of

FeCl 3 by nascent hydrogen

+3 Cl+H

Fe

+3 Cl+H.

The
ionic,

iron

is

i. e., it

reduced because the hydrogen becomes assumes a + charge.

Ionic oxidation

equation for stannous (tin)

and reduction are well shown in the the reaction between solutions of chloride and mercuric chloride (cf. 516).
Cl

Sn+2 Cl+Hg+2
182. Electrolysis.

Sn

+4 Cl+Hg I

the ionic point of view electrolysis of aqueous solutions is not the breaking up of the ionogen by the electric current: its molecules are dissociated

From

by the

solvent.

The battery

keeps the electrodes charged, and the ions move toward the electrodes; positive ions to the kathode The 61), and negative ions to the anode. (cf.
neutralization

charges by the electrodes into ordinary, unsubstances converts the ionic charged materials, which either escape, or react with
of

their

the

solution

(or

electrode)

according

to

their

properties.

ELECTROLYSIS.
Electrolysis of Acids.
(cf.

165

The

electrolysis of hydrochloric acid

128) gives hydrogen and chlorine. In the equation, the charge received from the electrode is put in parenthesis:

H+(-)+Cl+(+)
Here the primary products
without further change. Dilute sulphuric acid
is

H T +C1 T

of the electrolysis are set free

ionized according to the equation,

H S0
2

H+S0

4.

For

its electrolysis

the equation
4

is,

H+2 (-)+S0 +2
S0 4 +H 2

(+)

H T +S0

4.

The hydrogen

escapes, but the

S0 4
2

reacts with the water


4
.

H S0 +0 T
is

Hence the primary product S0 4


products the water that
2

H S0

+0.

Sulphuric acid

converted into the secondary is thus regenerated: it is


solution
is

is

decomposed.

Electrolysis of Bases. according to the equation,

Sodium hydroxide

ionized

NaOH 7
The
electrolysis equation
is,

Na+OH.

Na+(-)+OH+(+)
Each
of the

Na+OH.

primary products undergoes change:

Na+2 H

NaOH+2 H T

OH

H 0+0 T
2

Hence sodium hydroxide

is

regenerated at the kathode.

166

IONIZATION.

Electrolysis of Salts. trolyzed the equation is,

When

fused sodium

chloride

is

elec-

Na+Cl

|.

In the electrolysis of an aqueous solution the metal acts upon the water, giving sodium hydroxide and hydrogen.

Sodium

sulphate solution gives, as

we may

expect,

sodium and

while the secondary products are sodium hydroxide and hydrogen at the kathode, and sulphuric acid and oxygen at the anode.
as primary products,

S0 4

Cupric sulphate

is

electrolyzed according to the equation,


4

Cu+2 (-)+S0 +2
Copper
is

(+)

>

Cu I +S0 4
S0 4

water, giving

deposited upon the kathode, while at the anode. 2 S0 4

reacts with

+0

183. Electro-chemical Equivalents.

When
two

acids,

equal quantities of electricity are passed through any such as hydrochloric acid and sulphuric acid, equal

weights of hydrogen are liberated. Moreover, when hydrochloric acid is electrolyzed, hydrogen and chlorine are obtained in 76), i. e., 1.008 grams of equivalent amounts, by weight (cf.

water,

hydrogen for 35.45 grams of chlorine. In the electrolysis of hydrogen and oxygen are also obtained in equivalent
weights, viz., 1.008
:

8.

The same

current that liberates 1.008

hydrogen from sulphuric acid will set free 31.8 grams of copper and 8 grams of oxygen from cupric sulphate, and 107.94 grams of silver from silver nitrate solution. The equiv-

grams

of

alent weights obtained by electrolysis are thus the same as those found from combination.

184. Hydrolysis.

When sodium

hydroxide

is

neutralized

by hydrochloric acid, the union of water is all but complete, because, molecular to give

H+OH

HYDROLYSIS.
(1) (2)

167
(cf.
i.

the water

is

very slightly ionized

178),
e.,

and

the base and acid are both strong,

highly

dissociated, so that all their

OH

and

can unite.

Hence the

reverse action,

H 0+NaCl
2

NaOH+HCl,

very small. But when a salt formed from a strong base and a weak acid, e. g., sodium carbonate, is dissolved in water, the action of the ions of water is sufficient to give the solution a strongly alkaline
is

reaction.
2

Na+COa+2 H+2 OH

>

H CO +2 Na+2 OH.
2 3

The action

The
is

of the ions of water is called hydrolysis. cause for the hydrolysis of sodium carbonate
is

that the carbonic acid

weak,
of

i.

sociated into ions.

The union

e.,

slightly dis-

from the water

CO from the sodium carbonate, to give moleculeaves an excess of OH in the solution. lar H C0 A salt of a weak base and a strong acid, e. g., ferric
with
3 2
3,

chloride, is also

hydrolyzed;

only in this case free

acid,

i.

e.,

ionic hydrogen, is produced.

Fe+3 Cl+3 H+3 O~H

Fe(OH) 3 +3

H+3

Cl.

A salt of
(cf.

a weak base and a weak acid cannot exist


it is

in the presence of water:

478).
(cf.

The same

is

completely hydrolyzed true of compounds like

PC1 3

321).

Here two acids are formed.

168
185. Exercises.
1.

ON IZATION.

2.

Define acid, base, and salt in terms of the ionic theory. Write the ionic equations for the following reactions:

hydrobromic acid and potassium hydroxide; barium hydroxide and nitric acid; magnesium hydroxide and sulphuric acid; sodium carbonate and calcium chloride.
3. Cold, concentrated sulphuric acid does not act with zinc to give hydrogen, but the dilute acid does. Explain. 4. If we include the ions of water, what eight substances are

present in a solution of sodium chloride? very small amounts?

Which

are present in

5. The reaction of potassium cyanide and sodium phosphate (Na 2HP0 4 ) solutions is alkaline, and that of aluminum nitrate and cupric sulphate is acid. Write the ionic equations to " ex-

"

plain
6.

this.
is

What

the color of anhydrous

(recall

the color of

H S0 Na S0
2 4,
2

4,

Of CuCl 2 and Cu(N0 3 )2 solutions?


of the color of all three?

CuS0 4 ? Of S0 4 ions Of CuS0 4 solution? What is the common cause


etc.)?

Compare ordinary copper with


chlorate into

ionic

copper.
7.

How would

you change a

a chloride?

What

is

the other product? How would you test for a chloride? can you combine these tests to test for a chlorate?
8.

How

tell if it is

the table of quantitative solubility (Appendix viii) possible to make solutions of silver nitrate and sodium chlorate of such a concentration that silver chlorate will be precipitated

From

when the

solutions are mixed.

Is

it

possible for silver

nitrate

and potassium chlorate?

Explain.

CHAPTER

XVI.

NITROGEN AND THE ATMOSPHERE.


1 86. Existence of Nitrogen. Nitrogen is found uncombined chiefly in air, of which it makes up about 78% by volume and 75.5% by weight. It is found combined with many elements, as with hydrogen in ammonia, and with hydrogen and oxygen in nitric acid. Nitrogen is an essential constituent of all animals and of many plants.

Crude nitrogen may be prepared from air by the removal of the oxygen by means of phosphorus or copper. With phosphorus
187. Preparation.

the operation

is

as follows:
is

vessel (Fig. 40) of air

placed over a
in

phorus

which

is

floated

small dish upon water. The phosphorus unites with the oxygen
in
this

confined

portion of air

to form

which

is

phosphorus pentoxide, a white solid easily

dissolved

by the
is

water.

If

the

V>

experiment

carried out accu-

170

NITROGEN AND THE ATMOSPHERE.

The oxygen of air is removed more satisfactorily by hot copper. The apparatus is shown in Fig.
41.

Pure nitrogen

NH N0
4

may

2,

or, better,

be prepared by heating ammonium nitrite, a mixture of solutions of ammonium chloride

Water

FIG.

41.

(NH4 C1) and sodium nitrite (NaN02). When this mixture heated, a regular stream of nitrogen is evolved. The equations are
:

is

(1)

NH Cl+NaN0
4

(2)

(NH N0
4

2)

(NH N0 )+NaCl. N +2 H 0.
4 2
2 2

Pure nitrogen is taste, odor, color, and about 0.97 as heavy as air. 100 c.c. of water under ordinary conditions can dissolve only about 1 c.c. of the gas. One liter of nitrogen weighs about 1.25 g. under standard conditions, i. e., at C. and 760 mm.
1 88.

Properties of Nitrogen.

gas without

or

pressure.

CHARACTER OF THE ATMOSPHERE.

171

Since ordinary combustion and respiration require " oxygen, it naturally follows that atmospheric
nitrogen,"
i. e.,

air

deprived of oxygen, no longer

supports either combustion or respiration.

Pure

nitrogen, like atmospheric nitrogen, is an extremely inactive substance, combining directly with only a

few elements.

It does
etc.,

titanium, lithium,

combine with magnesium, at an elevated temperature,


.

3 2 giving nitrides, e. g., Under the influence of the electric spark, nitrogen unites with hydrogen and oxygen to form nitrous

Mg N

and

and with hydrogen alone to form hence these compounds, and the substances formed from them, viz., ammonium nitrite and ammonium nitrate, are found in the atmosphere,
nitric acids,

ammonia;

in water,

and in the

soil.

clover,

Bacteria living on the roots of some plants, such as peas and can take up nitrogen directly from the air, forming

albumins.

" CareAtmospheric Nitrogen a Mixture. ful experiment shows that a liter of atmospheric nitrogen weighs 1.2571 grams and one of pure
189.

"

nitrogen 1.2507 grams. The cause of this difference is that atmospheric nitrogen contains another subThus argon was stance, heavier than nitrogen.

discovered in 1894. N
190. Character of the

Atmosphere.

phere

is

the gaseous mantle of the earth.

The atmosSome of

172
its

NITROGEN AND THE ATMOSPHERE.


ingredients are practically constant in amount,
variable.

but others are

Constant Ingredients.
Nitrogen,

Variable Ingredients.

Water,

Oxygen, Argon, Helium, Hydrogen,

Carbon
Ozone,

dioxide,
*

Hydrogen
Dust,
etc.

peroxide,
nitrite,

Ammonium

and several rare and recently


discovered substances.
Bacteria are so universally present

ance to

may

and of such great importchanges taking place in the atmosphere that they rightly be classed among its variable ingredients.

many

By

pure air

we mean

a mixture of the constant

The proportions, constituents of the atmosphere. of the three most abundant and volume by weight, by
of these are as follows
:

BY VOLUME.
Nitrogen, 78.06%

BY WEIGHT.
75.5% 23.2% 1.3%

Oxygen, Argon,

21.00% 0.94%

Hydrogen
phere: 100
gen.

exists in small quantities in the

atmoshydro-

liters of it

contain about 19

c.c. of

Hydrogen is thus present in almost amount by volume as carbon dioxide (cf.

as great
193).

an

Nitrogen and oxygen, the most abundant constituents of air, have been described already. The rare gases of the atmosphere include argon, helium, neon, krypton, and xenon. These form a natural family (cf. 377) All are inert, and have a valence of o.
.

HELIUM.
191. Argon.

173
of

The discovery

argon almost took

place a hundred years before this substance was actually studied by Ramsay and Rayleigh in 1894;
for Cavendish, the discoverer of hydrogen, records

the observation that he could not get all the nitrogen " " of the air to combine with oxygen by sparking a mixture of these gases in the presence of potassium " residual nitrohydroxide. This was in 1785. The " and the other inert was argon gases which are gen

mixed with
Cavendish's

atmospheric nitrogen.
experiments,

By

repeating

Ramsay and Rayleigh

obtained argon.

A second way of obtaining this substance is to pass pure air over heated copper, which takes up the oxygen, and then over magnesium, which absorbs the nitrogen as magnesium nitride,

Mg N
3

2.

The

nitrogen

may

also

be removed by lithium or

calcium.

Argon may be condensed to a colorless liquid, 185 C., and at lower temperatures boiling at

may

form

even be obtained in the solid state. In gaseous It is much more it is heavier than oxygen. soluble in water than nitrogen, hence in air which has been dissolved in water and afterward expelled from solution the proportion of argon is greater than in the atmosphere. Argon is almost without chemical activity, hence its name.
the spectroscope, helium was discovered to be a constituent of the sun
192.
of

Helium.

By means

174

NITROGEN AND THE ATMOSPHERE.

a quarter of a century before it was known to exist on the earth. It has been found in small amount in
in

the earth's atmosphere, in certain rare minerals, some springs, and in a meteorite, as well as in the atmospheres of the sun and certain fixed stars. Like
argon,

helium

is

very

inert.

It

is

probably

less

soluble in water than

any

other gas.

193. Carbon Dioxide in the Atmosphere. --The chief variable constituents of the atmosphere are

carbon dioxide and steam, and to the presence of


these two substances

many

of the properties of the

atmosphere are due.


life
it

The atmosphere supports the

of chlorophyll-producing plants largely because

contains carbon dioxide.

The presence of carbon dioxide in the atmosphere may be shown by drawing a current of ordinary air through a solution
of calcium hydroxide (lime-water)
;

the white solid which sepa-

rates

from solution

is

calcium carbonate,

CaCOs

(cf.

283).

Under ordinary conditions, 10,000 parts, by volume, of air contain only 3 or 4 parts of carbon dioxide, Expired air contains 4%. If the air of a room contains 8 to 10 parts in 10,000,
it is

unfit to breathe,

both because of the carbon dioxide itself and of the decaying organic matter which is always exhaled along with it from the lungs. The quantity of carbon
dioxide in the atmosphere of a room thus serves as an index to the amount of poisonous material present.

ATMOSPHERIC DUST.
The
by the
great weight of the earth's atmosphere

175

may be

illustrated

fact that its carbon dioxide, although so small a proportion of the whole, is estimated to weigh over five million millions

of tons.

The Atmosphere. atmosphere is depends upon the temperature and the pressure. Air is saturated
194. in

Water Vapor

the

quantity of water vapor which the capable of holding at any given time

" with water vapor, or at the dew-point," when the reduction of temperature or increase of slightest

pressure causes precipitation of

some

of the water.

at 25 C. and at ordinary pressures over 2 grams of water. If the temperature falls to C., about 1.7 grams of the water are precipitated as rain. Usually the atmosphere is far from having all the water it can
liters of air

One hundred

can hold a

little

hold, only 60%, or less, of this amount being present on a fair day. If there is much more than this, we recognize its presence " " by the closeness of the atmosphere.

- - The 195. Atmospheric Dust. importance of atin dust certain mospheric causing phenomena is well

known.

sunrise colors, and helps to effect the precipitation of water vapor as An experiment to illustrate the clouds and rain.
It causes sunset

and

latter influence

is

the following :is filled

with dust-free air by drawing which has passed through a long through it, tube of cotton wool. If the room is now darkened, and a beam of light is directed through a small opening toward the flask, the beam will be visible in the outer air, but not in the flask, owing
large flask (Fig. 42)
for

some hours,

air

176

NITROGEN AND THE ATMOSPHERE.

to the absence of dust.

small

amount

of

steam

is

next

in-

troduced into the flask by connecting the flask at a with a vessel of boiling water, opening the pinch clamps at a and b, and sucking for a moment with the aspirator. A beam of light, directed as
before, will
visible

be practically
flask is

invisible.

The beam

will still

be

in-

when the

exhausted.

connected with the aspirator and partly small funnel is now attached to the tube at a,

To Aspirator

FIG.

42.

and a quantity of smoke is produced in the mouth of the funnel. This smoke is sucked into the large flask by opening the clamps at a and 6, and thus making connection with the aspirator. If now the clamp a is closed, and the air is slightly exhausted
through
b,

clearly visible

which

fill

of light passing through the flask will be owing to the small drops of water, i.e., mist, the flask. In a similar way the dust of the air probably

beam

causes the formation of drops of water.

196.

Weight and Pressure


of air

One

liter

Atmosphere. weighs, under standard conditions,


of the

LIQUEFACTION OF AIR.

177

and about
cause of

1.293 grams, and is, therefore, T f^ as heavy as water, 14.4 times as heavy as hydrogen. Beits

weight, the atmosphere exerts pressure

upon all bodies immersed in it. This pressure is measured by the height of the column of mercury the
atmosphere
will

support in the barometer (Fig.

9).

197. Liquefaction of Air.


air to the liquid condition is

same methods as those used to liquefy other " permanent " gases, and differs radically from the liquefaction of gases like ammonia, chlorine, and sulphur
dioxide.

The condensation of brought about by the

These gases
if

may

be condensed

at

ordinary

only sufficient pressure is applied; but gases like air cannot be liquefied at the ordinary temperature by any pressure, however great. Pressures
temperatures,

up

to thousands of atmospheres have been applied without avail. This is due to the fact that there is

for every gaseous substance a

maximum

temperathis

ture above which the gas cannot be liquefied; is called the critical temperature of the gas.

gas thus differs from an easily condensable gas in this respect, viz., that the critical temperature of a condensable gas is above the ordinary temperature, while that of the permanent gas lies far below the ordinary temperature. Such

"

permanent

"

air, hydrogen, etc., are, therefore, condensed only at a very low temperature and great pressure.

gases as

general methods are used to liquefy true gases. In the first method the gas to be condensed is first

Two

178

NITROGEN AND THE ATMOSPHERE.


its critical

temperature, and is then subIn the second method the gas is first strongly compressed, and is then cooled to its critical temperature. The second method has been used to liquefy air on a commercial scale.
cooled to
jected to pressure.

The apparatus consists of two pipes, either many yards long, the outer pipe forming a
inner one.

straight or coiled,

jacket about the

The

air is liquefied in the inner pipe.

By means

of

compressing

engines (Fig. 48) air is forced through

at a pressure of about 200 atmospheres. heats it, but it is cooled to the ordinary temperature,

the inner pipe Compressing the air

by running

The compressed air is water, before entering the liquefier. forced out of the inner tube, through a small opening controlled by a needle valve, into the outer tube. Here the pressure is low;
at one atmosphere. The compressed air thus expands and becomes cold for the expanding gas takes up the heat given off when it was originally compressed. In the outer tube the cold, expanded air passes back, around the inner tube,
it

may be

greatly,

cooling

The cooling effect, upon the compressed air, of the it. gas escaping, say, each minute, is small, but each new portion The of escaping gas is at a lower temperature than the last.
the temperature
cooling effect due to each expansion also becomes greater as falls. Finally the compressed air is cooled to the

temperature at which it liquefies, under the pressure used. The air escaping through the valve then contains drops of liquid air. These are caught in a part of the outer tube and drawn off into
storage vessels
(cf.

Fig. 43).

198. Properties of Liquid Air.

In the liquid con-

dition air

is

colorless,

water, and

boils at

has about the same density as 190 C., under ordinary pres-

PROPORTION OF OXYGEN IN AIR.


sure.

179

When

freshly

made, liquid

air is

about half

oxygen, but the proportion of oxygen increases by the evaporation of the nitrogen (liquid nitrogen boils about 10 C. below liquid oxygen) until the liquid
is

over

90%

oxygen.
preserved in open, double-walled vessels called The space between the walls of the bulbs
air

Liquid air

is

Dewar
is

bulbs (Fig. 43).

exhausted

of

to

conductivity of heat.
silk

secure nonTin or wooden


filled

boxes having double walls

with

may

also

be used.

Alcohol,
ide,

liquid

carbon diox-

etc., solidify when in liquid air, and steel placed burns in it like tinder; yet the

mercury,

hand may be held


short time

in it for a without injury, because protected by a non-conair in

ducting film of
state.

the gaseous
FIG. 43.

199. Determination of the Proportion of The amount of oxygen in a given in Air.


of air is usually

Oxygen volume

determined either

(1)

the oxygen, or

(2)

by exploding the

air

by absorbing with a known

volume

of hydrogen.

absorption method, a crude form of which was described under nitrogen (cf. 187), is carried out more accurately as follows:

The phosphorus

180

NITROGEN AND THE ATMOSPHERE.


analysis tube, partly full of
air, is
is

A gas

inverted in a hydrom-

eter jar (Fig. 5),

and the gas volume

carefully measured.

The

temperature
recorded.
-

A
of

pressure are thin stick of phos-

and

phorus
is

is

introduced into the tube

by means
left

a bent wire, and


is

there twenty-four hours.


residual gas

The phosphorus
and the

then removed, is measured.

When

the necessary corrections

CJ
FIG. 44.

EJ

have been made, the volume of oxygen absorbed and its per cent
of the original air are readily calculated.
pyrogallate

(cf.

The oxygen may also be absorbed by potassium 549) in a Hempel pipette (Fig. 44).
viz.,

The second general method, mixture of known volumes of

the explosion of a

air

and hydrogen,
trated as follows
:

may
-

be

illus-

lOcc.H

In

the

tube shown

straight eudiometer in Fig. 45, a known

10 cc. Air

volume
excess
electric

of ah- is

of

mixed with an hydrogen, and the


is

spark

passed through

the mixture.

All of the

oxygen
unite
FIG.
45.

of the air taken will thus

form water. with hydrogen The volume of steam formed will be equal to that of the hydrogen used up, but the volume of liquid water produced by the condensation of the steam will be
to

THE AIR A PHYSICAL MIXTURE.


insignificant.

181

Hence there

will

volume.

One-third of this contraction will


of

be a contraction of be the

volume
To
air

oxygen present

in the original air.


If

take a concrete example:

10

c.c. of

each of the gases,


after the

and hydrogen, are taken, the volume remaining


i. e.,

explosion will be about 13.7 c.c., Of this contraction 2.1 6.3 c.c.

the contraction will be

c.c.

hence 10

c.c.

of air contain 2.1 c.c.

= i of 6.3) are = 21%) of oxygen.


(

oxygen;

The proportions
of the

of the chief constant constituents

atmosphere have been determined in many different places, and have been found everywhere practically the same. This is a remarkable fact when

we remember

only a physical mixture, yet it is a necessary consequence of the circulation of the air and the rapid diffusion of its gases.
that air
is

That air is 200. The Air a Physical Mixture. not a compound of nitrogen and oxygen is proved by several facts, of which the following are illustrations
(1)
:

When nitrogen and


etc.

oxygen are mixed, there

is

no evidence

of union, such as evolution or absorption of heat, change of

volume,
(2)
it

were a chemical compound, like the nitrogen oxides, ought to have the same composition in the liquid state as in the gaseous. This, however, is not the case, as was stated in the
If air

description of liquid
(3)
its

air.

There

is

no reason

why

air, if

composition changed by solution in water; yet this

a compound, should have is the case.

182

EXERCISES.

Air that has been expelled from solution in water contains about 35%, by weight, of oxygen, instead of 23%, owing to the fact
that oxygen
is

much more

soluble than nitrogen.

20 1. Exercises.
Calculate the percentage composition of a mixture of gases, if 76 c.c. of the mixture contain 48 c.c. oxygen, 12.5 c.c. hydrogen, and the remainder nitrogen.
1.

2.

Why

is

not

all

the carbon dioxide at the earth's surface?


layer, in feet,

If it were,

how deep a

would there be?

(Cf.

193 and 278.) 3. It has been calculated that 900 grams of nitric acid

fall

every year upon an acre of ground. formed?


4..

Can you

suggest

how

it

was

16

c.c.

of

a mixture of nitrogen and oxygen were put with

25

c.c.

of pure hydrogen,
c.c.

and exploded.

The

residual gas

a volume of 23

How much

of the original mixture

had was

oxygen?
5 m. square?

How many liters of ah* are there in a room 3 m. high, and How much does it weigh at 20 C. and 740 mm.? How much of it is oxygen? How much of it is argon? How
5.
is

much
6.

carbon dioxide?

Explain
20

why

liquid air

becomes more and more blue on

standing.
7.
liters of air at

15

C. and 730

mm.

were passed through

lime-water, and the calcium carbonate (CaC0 3 ) formed weighed 0.0256 gram. How many c.c. of C0 2 were there in the 20 liters
of air?

CHAPTER

XVII.

AMMONIA.
202. Occurrence.

Ammonia

is

formed

in nature

by

the decay of organic compounds containing nitro-

gen,

and by

electric

discharges in moist air

(cf.

188), consequently ammonia and ammonium compounds occur in the atmosphere, in rain water, and Small amounts of ammonium comin the soil.

pounds are found

in plants

and

in

animal secretions.

Method of Preparation. In the is either ammonia made, (1) by heating laboratory, an ammonium salt with a base, or (2) by warming concentrated ammonium hydroxide solution. The ammonium salt in method (1) is usually the The base is generally slaked chloride or sulphate.
203. Laboratory

lime [Ca(OH) 2 ], or powdered sodium hydroxide. " Soda-lime," a mixture of sodium hydroxide and quicklime, is also used. The equations for the

double decomposition are:


2

NH4Cl+Ca(OH) 2

CaCl 2 +2

NH OH;
4
4

NH Cl+NaOH
4

NaCl
is

+NH OH.
and breaks up
2

Ammonium
readily into

hydroxide

unstable,

ammonia and water:

NH OH
4

NH T +H 0.
3

183

184

AMMONIA.

The first method of preparing ammonia may be carried out by mixing about equal parts, by weight, of ammonium chloride
and dry calcium hydroxide
"
(or

soda -

lime ") in a flask (Fig. 46), and heating the


flask

gently.

If

the

gas

is

wanted

dry, it is

passed through a bottle,


or U-tube, of quicklime or of coarsely broken

sodium hydroxide. Calcium chloride may not be used, because ammonia combines with it
to
FIG. 46.

give

crystalline

compound,

CaCl 2

NH

3.

Since water com-

bined in this
of the
tion."

" way is water of crystallization," the ammonia " compound may be described as ammonia of crystalliza-

and
"

126),

As in the case of chlorine and hydrogen chloride ( 114 we can tell when the gas of the collecting bottle (the
"

empty

one in the

figure) is

free

from
(here,

through this bottle into a solvent bubbles of gas are completely taken

up by making ammonia is to heat concentrated "ammonia water." Much ammonia is evolved. It

air by passing it water), until the the solvent.

The second method

of

may be dried as already described. Ammonia from Nitrides. Ammonia is also formed by 184) of many nitrides ( 188), e. g., Mg N hydrolysis (cf.
3 2
:

the

Mg N +6 HOH
3 2

Mg(OH) 2 +2
of

NH

204.

Commercial Sources

Ammonia,

The

two

chief sources of

ammonia

are:

PHYSICAL PROPERTIES.
(1)

185

The dry

distillation of

animal matter (bones,

skin-products, etc.).
(2)

The dry

distillation of soft coal.

Formerly all ammonia and all ammonium compounds were made by the dry distillation of animal " matter; hence the name spirits of hartshorn," " " " " hart spirit meaning a distillate, and being " The horns, bones, a general term for deer/' etc.
animals contain nitrogenous bodies, which give much ammonia when heated with quicklime without access of air.
hoofs, hides, hair, etc., of
This method
is

used in

many

places, especially since the old

method

of

making illuminating gas has been abandoned, to

convert into a valuable product almost worthless scraps of

animal matter.

The most common

source of

ammonia

for

many

years has been the wash liquors of the gas works. Gas is made in the old process by the dry distillation

At first it contains many them ammonia, hydrogen sulimpurities, among phide, and carbon dioxide; these are removed by passing the gas through water. When the wash
of soft coal
(cf.

297).

water, containing

ammonium

sulphide,

ammonium

carbonate, gas is evolved.

etc., is

heated with slaked lime, ammonia

Ammonia comes into the market as ammonia water (ammonium hydroxide) and also in the liquid state.
205. Physical Properties. less gas of characteristic odor,

Ammonia
One

is

a color-

liter of it

under

186

AMMONIA.
is

standard conditions weighs 0.762 gram; ammonia


therefore 0.59 as

heavy
is

as

air.
1

Ammonia
or 0.873

gas

very soluble in water:

c.c. of
c.c.

water absorbs, under standard conditions, 1,146

35%

gram of the gas. solution at 15 C. is

The

specific gravity of a

so-called 28

about 0.88; that of the Beaume solution is about 0.90.


into cold water as into a vacuum,

Dry ammonia rushes

and

is

likewise very soluble in alcohol


of

and

in ether.

Charcoal can take


its

up under favorable conditions about ninety times

own volume

ammonia

gas.

206. Liquefaction

of

Ammonia.
is

The

critical

temperature of

ammonia

far

above the ordinary

AffC1.2NH

FIG. 47.

temperature, hence the gas


pressure.

may

be liquefied by

simple apparatus for condensing amin Fig. 47.


of the

monia

is

shown
amount

small

compound which

silver chloride

forms

with ammonia, viz., AgCl. 2 is placed in the rounded end 3 of the bent tube. The tube is then sealed, and the end containing the silver ammonium compound is warmed in a water bath, while the drawn-out end is cooled in a freezing mixture. The
,

NH

compound containing the ammonia is thus decomposed, and the ammonia is condensed in the drawn-out end.

AS A REFRIGERATING AGENT.
Liquid
freezes at

187

ammonia
40

is

about 0.6 as heavy as water.


pressure,

It boils at

-75

C. under ordinary C.

and

207. Liquid

The

chief use

Ammonia as a Refrigerating Agent. of liquid ammonia is as a refrigerating

Expansion Valve Brine Tank.

Compression

Expansion Coils and Ice Molds.


FIG. 48.

Pump.

agent,

and
is

to produce artificial ice.

For

this

purpose

gaseous ammonia (produced by heating ammonia


water)

ammonia
is

condensed to the liquid state, and the liquid is then allowed to evaporate rapidly. The

heat necessary for the vaporization of the


absorbed from the body
to be cooled.

ammonia

The apparatus shown


ciple,

in Fig. 48 gives, in prin-

the construction of a refrigerating system.

188

AMMONIA.

The compression engine forces gaseous ammonia into condensing pipes (cooled by streams of water) under so great a pressure that the ammonia is liquefied. The liquid ammonia
is

by a

then allowed to expand in another system of pipes surrounded brine of concentrated salt solution or of calcium chloride

solution.

These

may

be cooled to

-21

C. and

-48

C., re-

When tanks containing water spectively, before they freeze. are placed in the cold solutions, the water is frozen.
Instead
of

ammonia,

liquid

sulphur
air, etc.,

liquid carbon dioxide, compressed used to produce artificial ice.

dioxide, are often

burn

208. Chemical Properties. Ammonia does not in the air, but it burns readily in oxygen.
2

NH +3
3

H 0+N
2

2.

Ammonia
the nitride

reacts with heated 188)


3

(cf.

magnesium, giving and hydrogen,


>

NH +3 Mg

Mg N +6 H T
3

Chlorine reacts energetically with

ammonia, form-

ing nitrogen and hydrogen

chloride.

The equation

is,

NH +3 Cl
3

N+3

HC1.

If

the

ammonia
some
is,

is
it,

present in excess, the hydrogen chloride

unites with

of

forming

ammonium
3

chloride.

The com-

plete equation

therefore,

NH +3 Cl
3

NH C1+N.
4

A similar reaction

occurs between

ammonia and bromine.

AMMONIUM HYDROXIDE.

189

Gaseous ammonia and hydrogen chloride unite in equal proportions by volume to form solid ammonium
chloride.

When ammonia 209. Ammonium Hydroxide. dissolves in water, the solution contains ammonium
hydroxide:

NH +H
3

NH OH.
4

The hydroxide

is

ionized like
~
4

any base

(cf.

175)

NH OH
4

NH +OH.

slight;

The conductivity of the solution is, however, very hence we conclude that the concentration

very small. This may be due to hydroxide is not readily dissociated (weak base); or it may be that most of the ammonia is merely dissolved in the water, but not combined with it. When ammonium hydroxide is treated with a strong acid, the salt produced is
of
4

NH +OH

is

the fact that

ammonium

neutral
is

Judged by

this test,

ammonium
is

hydroxide

a strong base.

The discrepancy
is

plained.

When

an acid

added,

its

readily exions remove


ionization

ions present, consequently of molecular takes place. 4

the

OH

more
2

NH OH of NH OH molecules, NH supply until all the NH is used up.


4 3

To keep up

the

and

HO

combine

The
and

solution then
its ions.

contains only the


4

ammonium

salt

NH +OH+H+C1

NH +C1+H O.
4 2

190

AMMONIA.

Because of its basic properties, ammonia water is used in cleaning, to remove grease and acids, and to
soften water
210.
(cf.

70)

Ammonium

Salts.

Ammonium

salts

are

made by
acids
(cf.

the neutralization of the hydroxide by 160), or by the direct union of ammonia


e. #.,
3

with the acids,


4

NH OH+HN0 NH +HN0 2 NH +H S0
3

NH4N0

+H 0.
2
.

NH N0
4

3.

(NH4 S04
)2

All the
solutions.

common ammonium
The group
its

salts are white,

and form

colorless

NH

has not been obtained as a substance,

because

it

breaks up into

ammonia and hydrogen

(cf.

427)

compounds are like those of the metals, it is called ammonium and is treated as a metal radical (cf. 105 and 160). In ammonia the valence of the nitrogen is 3. In the ammonium compounds two univalent groups are added, raising the valence to 5. The accompanying table shows the resemblance between the formulas of ammonium compounds and those of sodium and
but, since

potassium.

DISSOCIATION OF COMPOUNDS.
211. Dissociation of

191

In solution,

Ammonium Compounds. ammonium salts are dissociated like


:

those of the metals

NH C1 ^n NH
4

+C1.

(NH4 2S0 4
)

;=

NH +S0
4

4.

heated, giving ammonia, on the one hand, and acids, or acid salts, on the other. See, however, ammonium
nitrate,

Ammonium

salts are also dissociated

when

238.
4

NH T +HC1 1 > NH H +H C0 (NH C0 2 NH T +H P0 (NH HP0 - NH 1 +NaH P0 NH NaHP0


3
.

NH C1
4) 2

3 (i.

e.,

+C0

2 T ).

4) 2

4.

4.

The temperature
For
4 4

of

dissociation varies greatly.


is

NH C1, dissociation complete above 350 C.; hence, NH C1 does not exist, under ordinary pressure,
above
of

When all the products temperature. the dissociation are volatile, as in the case of
this

ammonium

chloride

and carbonate, they reunite

when they become sufficiently cool. Such salts are sublimed by heat. Sublimation is the distillation of
a
solid.

When

the acid (or acid salt)

is

non-volatile,

as in the case of

ammonium phosphate and ammo-

nium sodium hydrogen phosphate, there is no sublimation; only the ammonia passes off (see 357).

192

AMMONIA.
Ammonia.

212. Composition of
sists of

Ammonia

con-

nitrogen and hydrogen united in the proportion, by weight, of 14 parts nitrogen to 3 parts hydrogen. This fact is indicated by the formula

NH

3.

The volumetric composition


-

of

ammonia may be

proved in several ways: (1) By synthesis from nitrogen and hydrogen. (2) By the action of chlorine on ammonia.
213. Synthesis of If the Hydrogen.
gen, mixed

Ammonia from Nitrogen and


two
gases, nitrogen

and hydroof nitrogen

in the proportion of 1

volume

to 3 of hydrogen, are subjected to the electric discharge, they combine in part to form ammonia;

the union cannot, however, be made complete, no " " matter how long the is continued. sparking This is due to the fact that a point is soon reached at which as much of the ammonia is decomposed in a given time as is formed in the same time by the union of nitrogen and hydrogen.

N+3 H '
To make
to
This

NH

3.

the combination complete,


it is

it is

necessary

remove the ammonia as fast as


may

formed.

" be done by " sparking the mixture of nitrogen and hydrogen over some substance, e. g., sulphuric acid, capable
of

removing the ammonia.

It is thus proved that 1 volume of nitrogen unites with 3 volumes of hydrogen to form ammonia. The

ACTION OF CHLORINE.

193

union is accompanied by a shrinkage in volume, 4 volumes of the mixed gases becoming 2 volumes of

ammonia

(cf.

140).

volume
128),

Since 1 214. Action of Chlorine on Ammonia. of chlorine unites with 1 of hydrogen (cf.

the relation of

nitrogen to

hydrogen can be obtained readily if that of nitrogen to chlorine can be established. For this purpose we

make

use of

the

known
is

action
(cf.

of

chlorine

upon ammonia

The experiment follows :

carried

208). out as

A Hoffmann tube (Fig. 49) is filled first with a saturated solution of sodium chloride in
water, and then,

by displacement

of the salt

solution, with chlorine.

The stopcock is then closed, and the cup above the stopcock is filled with concentrated ammonium hydroxide solution. The latter is now run, drop by drop, into the chlorine, care being taken that no air enters and no
chlorine escapes. flash of light will be seen of ammonia water are introduced. drops

F IG

49.

when the
in,

first

When
stopcock

almost
is

all

of the

ammonia water has been run

the

and the cup is filled with water. The cup is now connected, by means of a tube filled with water, with a
closed

beaker of dilute sulphuric acid, the stopcock is again opened, and the water and dilute acid are allowed to enter until the
pressures inside and outside the tube are equalized.

194
The
tube,

AMMONIA.
which was
full of chlorine, will

now
::

be one-third full

of nitrogen.

Hence,
of nitrogen
of nitrogen
: :

Volume Volume

volume volume

of chlorine of

1
::

3;
:

whence

hydrogen

3.

215. Exercises.
1.

How many

grams of ammonia can be made by heating


chloride with slaked lime?

100 grams
liters at

ammonium

How many

30 C. and 720 mm.?

2. What weight of ammonium sulphate is required to give, with lime, 20 liters of ammonia at 15 C. and 680 mm.?

3.

What

weight of slaked lime, Ca(OH) 2

is

necessary to de-

compose 50 grams ammonium nitrate? ammonia will be formed?


4.

How many

grams

gas?
5.

May concentrated sulphuric acid be used to dry ammonia May phosphorus pentoxide? Why? How could you separate a mixture of the gases ammonia,
What would be the volume of each of the resulting gases c.c. of ammonia were completely decomposed into its

oxygen, hydrogen, and nitrogen so as to get the proportionate amounts of each in the mixture?
6.
if

500

constituents?
7.

How many

to unite exactly with the hydrogen produced decomposition of 100 c.c. of ammonia?
8.

cubic centimeters of oxygen will be required by the complete


tell

Give the uses of ammonia, and

upon what property

each use depends.

CHAPTER

XVIII.

MOLECULAR FORMULAS AND EQUATIONS.


In 142 we learned 2 1 6. Molecular Equations. that reasoning based upon Avogadro's hypothesis leads to the conclusion that the molecules of hydrogen,
chlorine,

oxygen,

and nitrogen contain two


(cf.

atoms each.

Now,

in the free state these elements


98).

exist as molecules,

not as atoms

Hence,

when the gaseous elements appear in molecular formulas (H 2 C1 2 O 2 and


, ,

equations, the

2)

should be

used.
of all

Equations containing the molecular formulas the gases in the reaction are called molecular

equations.
lar

Some

illustrations will

show how molecu-

equations are evolved from the ordinary ones. Thus, to form the molecular equation for the

action of zinc
(1)

upon sulphuric

acid,

We write the simplest possible equation, showand formulas


of the materials

ing only the symbols

used and produced: Zn+H 2S04


(2)

ZnS04 +H T
:

We

balance the equation

Zn+H S0
2

ZnS0 4 +2

HT

(3) Since free hydrogen exists as molecules,

we

write,

Zn+H S0
2

ZnS0 4 +H 2 T
195

196

MOLECULAR FORMULAS AND EQUATIONS.

In this equation there is no comparison between the volumes of reagents or products, since only one, hydrogen, is a gas. However, since the formula

(2.016 g.),
i. e.,

represents a gram-molecular weight of hydrogen it also represents a gram-molecular volume,


22.4 liters, under standard conditions.

the molecular equation (3), therefore, a direct comparison between the weight of zinc and sulphuric acid used, and the volume of hydrogen

From we can make

obtained: 65.4

<7-

zinc liberate,

22 J+

liters

of hydrogen.
of

in oxygen.

As a second illustration we may take the burning The three equations are
(1) (2) (3)

carbon

C+0C+2

-C0
:

C0

C+0

of

Equation (3) shows that 1 volume of oxygen gives 1 volume carbon dioxide; or, using the gram-molecular weights and
it

volume, we read
12
g.

thus

C+32

g.

(22.4 liters)

44

g.

C0

(22.4 liters).

The carbon is not gaseous, hence its volume is* not indicated. The third illustration of molecular equations is the one for the
burning of alcohol vapor (1) The skeleton, or framework, of the equation:
:

C
(2)

H 0+0
6 6

The

balanced equation:

C H 0+6
2

(3)

The molecular equation:

C 2H6 0+3 O 2

C0j+H 0;
2

C0 +3 H 0;
2 2

CO +3 H 0.
2

DETERMINATION OF A FORMULA.
Since
all

197

that 1 volume of alcohol vapor

molecules occupy the same space, this equation means 3 volumes of oxygen (at the

same temperature and pressure) give 2 volumes

of carbon dioxide

+ 3 volumes of steam.
The simplest 217. Determination of a Formula. formula that can be assigned to a compound is determined from its percentage composition and the atomic weights of its elements. If the molecular weight of the compound can be obtained, we can decide whether the simplest formula is also the
correct formula, or whether some multiple of the simplest formula must be taken. If the molecular

weight cannot be found,

we

use the simplest formula.

Some

illustrations will explain the

method.

Formula

of

Silicon

Dioxide.

The percentage
-

composition of silicon dioxide


Si,

is,

47.02%;
52.1

0,

This means that the weight of


all

all

the silicon atoms

in the molecule of silicon dioxide is to the weight of

the oxygen atoms as 47.02 is to 52.98. Now, the relative weights of the atoms are represented by the atomic weights. Hence, if we divide the per cent of

each element

in

the molecule of silicon dioxide

by

the atomic weight of the element,

we

get the relative

numbers of atoms present.


Relative Relative

number
number

of Si
of

atoms =

V
5

'

B 4

= 1.655.

atoms = -^-=3.31.

198

MOLECULAR FORMULAS AND EQUATIONS.

But there must be whole, not fractional, numbers atoms in the molecule. We find that the ratio ^ff- becomes | if both terms are divided by the smaller, 1.655. Hence there are twice as many atoms of as of Si, and the simplest formula is Si0 2 As the molecular weight cannot be determined by the methods available (why?), this is the formula used.
of
.

Ethane is composed of carbon, 80%, Formula of Ethane. and hydrogen, 20%. A liter of it weighs 1.34 g. under standard conditions. Find its formula. The relative number of carbon and hydrogen atoms is found by dividing the per cent of each

by the atomic weight


Relative
Relative

of the element. of of

number number

atoms = if = 6.67.

H atoms = ^=20.00.

ratio %V- becomes i if we divide both terms by 6.67. Hence there are 3 hydrogen atoms in the ethane molecule for The every carbon atom, and the simplest formula is CH 3 molecular weight of ethane, as found from the weight of 1 1. 143 and 145), is 30, while that corresponding to CH3 (cf. would be 15; hence the simplest formula must be doubled. The

The

formula of ethane is C 2 He. Formula of Ether. The composition of ether is: C, 64.86%; H, 13.51%; O, 21.62%. The vapor is 2.31 times as heavy as
oxygen.

number Relative number Relative number


Relative

of of

of

atoms = 54ir = 5.405. atoms = -^^-=13.51. atoms = ^4r1== 1-35.

By dividing each of the three numbers by 1.35 we see that they are related as 4 10 1. The simplest formula of ether is, there:
:

fore,

C 4 Hi

O.

The molecular weight

is

about 74

(i. e.,

2.31 X32).

This corresponds to that of the simplest formula.

POLYMERS.
2 1 8. Constitutional Formulas.
If

199

we know

the

molecular formula of a compound, and the valence of its elements, we may represent the way in which the atoms are joined in the molecule by means of

do those of hydrogen chloride and hydrogen, the atoms are assumed to be joined directly, and the constitutional formulas are H Cl and H H. Here the combining power (valence) of each atom is represented by a single line, or bond. In the case of the water

constitutional, or structural, formulas. molecules consist of two atoms each, as

When

the

molecule

we assume

that the two hydrogen atoms

The oxygen are united to the one oxygen atom. of have its atom seems to holding other atoms power
directed along two lines, or valences, each of which can hold the single valence of a hydrogen atom. In

same way the nitrogen atom of ammonia is united with each of the three hydrogen atoms, and the carbon atom of marsh gas with each of the four carbon atoms (cf. 132) The constitutional formulas
the
.

of these substances are

H
H-O-H,

H
andH-C-H.
I

H
219. Polymers.

/ \

different molecular weights, are said to

Substances that have the same percentage composition, but be polymers of one an-

200
other.

MOLECULAR FORMULAS AND EQUATIONS.


Thus, formaldehyde,
acetic acid,
:

and grape sugar have the

same

percentage composition

C = 40.00%.

H=

6.67%.

0-53.33%.
The simplest formula for each is, therefore, CH 2 0. A substance having this formula must have a molecular weight of 30. This is the molecular weight of formaldehyde. The molecular weight
of acetic acid is 60, and that of grape sugar, 180; hence these substances are the di-polymer and hexa-polymer, respectively, of formaldehyde, and their formulas are C 2 4 02 and C 6 Hi 2 6

220. Isomers.

Many

cases are

known

in

which two or more compounds have

the same composition and molecular weight, but different properties. Methyl ether and ethyl alcohol, for example, are both represented

by the formula C 2 H 6 0; these substances are

so differ-

ent, however, that no one would mistake one for the other. Thus 24 C., at ordinary pressure, while ethyl methyl ether boils at alcohol boils at +78 C. Such compounds are said to be isomers

of one another.

ences between isomers


the molecule.

Constitutional formulas represent the differby different arrangements of the atoms in


is,

Thus, the structural formula for methyl ether

H
I I

H
I I

H-C-0-C-H; H H
while that of alcohol
is,

H H
I

H-C-C-0-H.
I I

H H

EXERCISES.

201

According to these formulas, all the hydrogen atoms of methyl ether have the same relation to the remainder of the molecule and
should behave in the same
of ethyl alcohol one
case; for the

way with

hydrogen atom should be different from the other

reagents; while in the case the one bound to oxygen

of the six

five. This is actually the hydrogen bound to oxygen is the only one that can be replaced by sodium and other metals.

atom

of

221. Exercises.
1.

Write the molecular equations for the following reactions

(a)
(6)
(c)

(d)
(e)

(/)

(g)

(h)
(i)

hydrogen and chlorine. Burning of hydrogen in air. Union of nitrogen and hydrogen to give ammonia. Action of sodium upon hydrogen chloride. Burning of ethane in air. Union of ammonia and hydrogen chloride. Burning of ammonia in oxygen. Decomposition of potassium chlorate by heat, Reaction of zinc with hydrochloric acid.
of

Union

2.

A
its

liter of

a gas weighs 1.96


is:

g.

and
3.

composition

C, 27.27%;

under standard conditions, Find its 0, 72.73%.

formula.

certain gas consists of N,


g.

weigh 0.3932 formula?


of
it

63.64%; 0, 36.36%. 200 c.c. under standard conditions. What is its


C,

4.

certain

compound has the composition:


Its

H, 13.04%; 0, 34.78%. oxygen. Find its formula.


5.

vapor

is

1.44 times as

52.17%; heavy as

A compound has the composition: C, 10.04%; H, 0.84%; 0.26 g. of it had a volume of 70 c.c. at 99 C. and 89.12%. Cl, under 740 mm. pressure. What is its formula?
6.
is:

A compound

C, 83.33%; H, 16.67%.

has a molecular weight of 72. Find its formula.

Its

composition

CHAPTER

XIX.

NITROGEN ACIDS AND OXIDES.


222. Nitric Acid.
Nitric acid
is

one of the most

important substances known to Chemistry. It has been in use since the time of the early alchemists,

but

its

true nature

was not understood


nitric acid

until the

latter part of the eighteenth century.

During the Middle Ages


niter.

the distillation of a mixture of

was made by alum, blue vitriol, and

Alum is potassium aluminum sulphate plus crystal water [K 2 S0 4 A1 2 (S0 4 )3, 24 H 2 0], and blue vitriol is cupric sulphate by the dry distillation of plus crystal-water (CuS0 4 5 H 2 0) these substances sulphuric acid was set free. This with the niter
,
.

(KNOs) gave

nitric acid.

223.

time

nitric acid is

At the present Commercial Preparation. made on a large scale by heating


acid.
is

sodium nitrate with concentrated sulphuric

The operation
of glass tubes
redistilled.

and the vapors evolved are condensed


(Fig.

carried out in large iron retorts; in a system


50).
202

The

resulting liquid

is

LABORATORY METHOD
In this

203

way there is obtained an acid of specific gravity 1.4; " " boiling point is 120 to 121 C. commercial This, the grade of nitric acid, is only 68%, by weight, nitric acid. The
its

remainder

is

water.

FIG. 50.

224. Laboratory
nitric acid is

Method.

In

the

laboratory,

commonly made by
concenacid

heating potassium

nitrate

with

trated sulphuric

in a retort or distilling

bulb connected with a condenser. The condenser

may be a flask kept cold by running


Fig. 51.

water, as in
distills over,

When no more

acid

FIG. 51.

H2

the retort is allowed to cool; the other product of the reaction, potassium hydrogen sul-

204
phate

NITROGEN ACIDS AND OXIDES.

(KHS0

4 ),

then crystallizes out in the form of

long, white needles. The equation for the reaction

is,
4 3

KN0 +H S0
3 2

KHS0 +HN0

phuric

For the reaction between sodium nitrate and acid the


equation
2 4

sul-

is,

NaN0

+H S0

NaHS0

+HN0

225. Preparation of Nitric Acid Compared with The preparation of that of Hydrochloric Acid. In nitric acid resembles that of hydrochloric acid.

each case the acid is set free from its salts by sulphuric acid, not because sulphuric acid is stronger than the acid it displaces, but because hydrogen chloride

and

nitric acid are volatile,

and

are, therefore, re-

moved from

the

"

field of action."

As a

result, the
(cf.

reaction goes on until practically complete

213).

acid
is

In each of these cases only half of the hydrogen of sulphuric If the temperature is replaced by the metallic element. raised considerably, a second portion of sodium nitrate will

react with the

sodium hydrogen sulphate formed, giving normal sodium sulphate and a second portion of nitric acid, according

to the equation,

NaNOs+NaHS0
commercial
nitric acid,

Na S04 +HNO
2

3.

In the treatment of sodium chloride with sulphuric acid on a scale, this second reaction is actually carried out, because the compound Na 2 S0 4 is wanted. In the preparation of
however, the second reaction
is

of

no advantage,

since the high temperature necessary decomposes the nitric acid.

ACTION OF NITRIC ACID.


226. Properties
nitric acid is

205
Commercial

of

Nitric

Acid.

with concentrated sulphuric acid. The anhydrous acid (the best yet made was probably 99.8% pure) is a thick,

dehydrated by

distilling it

colorless oil of specific gravity 1.56.


distill

It begins to

at 86

C.,

but

is

largely

decomposed

in the

operation.

HN0

N0

(or

4)

+H O+O.
2

Under reduced pressure (c/. 340) it distills undecomposed. Nitrogen dioxide is a brown gas which dissolves readily in
hence anhydrous nitric acid that has been under ordinary pressure has a brown color. This color removed by bubbling air through the liquid.
nitric acid;
distilled

may

be

The same decomposition


(very rapidly in sunlight)
;

hence the

of nitric acid takes place in the light nitric acid of reagent bottles

soon becomes brown.

When the vapors of nitric acid are passed through a hot tube they are completely decomposed into nitrogen dioxide, water, and oxygen.
As an
acid,
nitric

acid neutralizes solutions of

bases, forming with them nitrates and water, just as hydrochloric acid forms chlorides and water.

tendency of

The 227. Action of Nitric Acid upon Metals. nitric acid to break up into oxides of

nitrogen and free oxygen (cf. 226) determines its chemical for nitric acid is not only general behavior;

a strong acid, but a powerful oxidizing agent.


therefore,

When,

we compare

the action of nitric acid upon

206

NITROGEN ACIDS AND OXIDES.

metals with that of hydrochloric and dilute sulphuric acids, we observe a great difference; for while the
acids just named generally give up hydrogen when treated with metals, nitric acid rarely does so.

Instead of setting hydrogen free, the metal usually reduces some of the nitric acid to nitrogen oxides
or,

even lower, to hydroxylamine,

NH OH,
2

and

to

ammonia.
The reaction of copper with dilute nitric acid is typical. The products are cupric nitrate, water, and nitric oxide (cf. 237).
3

Cu+8 HN0

Cu(N0 3 ) 2 +4

H 0+2 NO T
2

The stages of the reaction are probably as follows: (1) The decomposition of nitric acid according to the
equation:

general

HN0

H 0+2 NO+(3
2

0).

(2)

Oxidation of copper to cupric oxide:

3Cu+(30)
(3)

The

reaction of cupric oxide and nitric acid

(3

CuO)+6

HN0

(3CuO).
(cf.

162)

Cu(N0 3 ) +3
2

H 0.
2

(4)

The complete equation, given above,

is

made by com-

equations, the intermediate products (in parentheses) being eliminated. For silver and nitric acid the equation is similar, except that

bining the partial

the metal

is

univalent,
3

Ag+4 HNO

> 3

AgN0 +2 H 0+NO T
3
2

OXIDATION BY NITRIC ACID.

207

Zinc and dilute nitric acid (5% to 6%) give zinc nitrate, water, and ammonium nitrate. In this case hydrogen may be an intermediate product.
(1)

If so,

the probable equations are:


3

Zn+2 HNO
4

Zn(NO 3 +(H
)2 3

2 ).

(2)

Zn+8 HN0
(1)
3

>

Zn(N0
4.

3) 2

+(4

2 ).

This

is

equation
(3)

multiplied
2)

by

HN0

(4)

H (NH OH)+HNO
+(4
4

(NH4 OH)+2
3

H 0.
2

NH N0 +H O.
4

Hence the complete equation is,


4

Zn+10

HN0

Zn(N0

3) 2

+NH N0 +3 H 0.
4 3
2

The reduction
addition of a

of nitric acid to

ammonia can be shown by

the

little

of the dilute acid to a


(cf.

warm
447).

mixture of zinc

dust and sodium hydroxide solution

Gold and platinum alone of Aqua Regia. more common metals do not react with nitric acid. As was stated under Chlorine (cf. 116), these in chlorine in and soluble are two metals aqua regia
228.
all

the

water.

Aqua

regia

is

made by mixing

nitric acid

with

hydrochloric acid to one of

acid

(three volumes of hydrochloric nitric acid); it is merely a source of

nascent chlorine.

Aqua regia is used to dissolve besides gold and platinum.

many

other metals

It is not only 229. Oxidation by Nitric Acid. an oxidizing acts as toward metals that nitric acid

208
agent.
acid,

NITROGEN ACIDS AND OXIDES.


Phosphorus is converted by it into phosphoric and sulphur into sulphuric acid.
2 HN0 H O+2 NO-f (3 0). H 0+S+(30) H S0
3 2

4.

Glowing charcoal burns in the acid much as it would in oxygen itself. Organic coloring matters, e. g., indigo solution, are oxidized by nitric acid to
colorless bodies.

The

oxidizing

power

of nitric acid

is

much

greater

if

some

of

the higher oxides of nitrogen are present. Such an acid is fuming nitric acid, a red liquid containing much nitrogen dioxide, 2 This acid is used for very rapid oxidation.

N0

It

is

instability.

evident that the oxidizing action of nitric acid is due to its One of the products is always water; the oxides of

nitrogen produced are decomposition products of nitrogen pentThe following equations oxide, the anhydride of nitric acid. of of some the the stages decomposition: represent
(1) (2) (3) (4)

HNO HN0 2 HN0 2 HN0


2 2

3 3

3
3

H 0+N +0. H 0+N +2 0. H 0+2NO+3 0. H 0+N +4 0.


2 2

4
3

Which of the nitrogen oxides will be formed depends on the concentration of the acid, the temperature, and the reducing agent. Equation (1) represents what occurs when concentrated
nitric acid is heated, or treated

with metals.

Equation

(2) is

for the action of starch, arsenic trioxide, etc., with acid of specific gravity 1.3. Equation (3) is for copper, silver, etc., and acid of
specific gravity 1.2.

Equation

(4) is for zinc

and

nitric acid of

specific gravity 1,1.

SOURCES OF NITRATES.

209

All nitrates, like nitric acid, are 230. Nitrates. and as act unstable, 25). All oxidizing agents (cf. but those of sodium, potassium, and ammonium
(cf.

234 and 238) break up, when heated, essen-

acid (cf. 226), except that the oxide of the metal is formed instead of water. Cuprk nitrate is an example tially like nitric
:

Cu(N0

3) 2

CuO+2 NO +O
2

(cf.

236).

231. Sources

of

Nitrates.

When

electric

dis-

charges pass through air, some (NO) is formed. This reacts with water and oxygen, giving
nitric oxide nitric acid:
2 3

NO+O
2
2

2 2

N0 +H

N0 HN0 +NO.
2. 3

probably formed in this way, In imitation of and gets into the soil (cf. 188). this method some nitric acid is now being prepared by the action of powerful electric arcs upon air.
nitric acid is

Much

This process of synthesizing nitric acid is very important, in view of the fact that nitrates are used extensively as fertilizers
(cf. 358), and that the natural supply is very limited. most extensive nitrate deposits are those of sodium nitrate

The
(Chili

saltpeter)

beds
(cf.

"

Nitrate found in the Atacama Desert, in Chili. were probably formed by the action of oxidizing bacteria

"

upon nitrogenous organic substances, in the presence of In certain parts of Europe farmers cultivate nitrates by adding the proper bacteria to a mixture of alkali and nitrogenous matter.
25)
alkali.

210

NITROGEN ACIDS AND OXIDES.


solu-

tions of

Potassium nitrate is made by mixing hot, concentrated sodium nitrate and potassium chloride.

NaN0 +KCl
3

KN0 +NaCl I
3

The sodium

chloride
is

is

filtered off while

the mixture

is

hot.

When

the filtrate

cooled, almost pure potassium nitrate

crystallizes out.

Potassium nitrate was formerly obtained almost entirely from In the neighborhood of cities a deposit of calcium nitrate appears on the ground. This is collected, and the solution is treated with wood ashes, which contain potassium carbonate
Asia.

(#.422).

Ca(N0 )2+K 2 C0
3

CaC0

+2 KN0

3.

232. Uses of Nitric Acid and the Nitrates. Nitric acid is used in making sulphuric acid by the " Chamber Process " (cf. 262), and in making " nitrobenzene, nitroglycerine," collodion, guncotton, celluloid, etc.
Glyceryl nitrate (wrongly called nitroglycerine) is made by the action of a mixture of concentrated nitric and sulphuric acids at a low temperature upon glycerine. It is a thick, greenish
liquid of

a very unstable nature, and very explosive. It is usually mixed with a porous earth, and appears in the market chiefly
as dynamite.

Gun cotton and They are made by

collodion are nitrates of cellulose

(cf.

548).

the action of a mixture of nitric and sulphuric acids upon cotton. Gun cotton is used as an explosive. It is not soluble in a mixture of alcohol and ether, while collodion the solvents evaporate, the collodion is left as a tough, transparent layer. It is used to make photographic films, and
is.

When

NITROUS ACID.
to protect wounds from the cotton and camphor.
air.

211
is

Celluloid

a mixture of gun

Nitrobenzene
sulphuric
acid

is

made from
it

mixture.

When

benzene, C 6 6 and the nitricnitrobenzene is reduced by


,

nascent hydrogen,

gives aniline, the starting material in the

manufacture of the aniline dyes. The nitrates are used in the manufacture of gunpowder

and various
"

explosives, in the preservation of meats, e. g., corned beef," and as fertilizers. Gunpowder is a physical mixture of potassium nitrate, sulphur, and charcoal, in various
26). The relative amounts of the constituents proportions (cf. vary, according to the purpose for which the powder is to be used. When gunpowder is ignited, it forms gases that occupy several hundred times as much space as the original powder.

The

reactions taking place in the explosion of one kind of

gunpowder are probably represented by the equation,


2

KN0 -hC+S
3

K S0 +C0 +N
2 4

2.

Another equation
2
3

is

KN0 +3 C+S

>

K S+3 C0 +N
2

2.

("

233. Nitrogen " =

Pentoxide.
is

Nitrogen

pentoxide

penta
it

cause

is

of theoretical importance bethe anhydride of nitric acid, i. e., it is


five)

nitric acid

minus water.
is

The
2

relation of nitrogen

pentoxide to nitric acid

evident from the equation,

NO +H
2
5

HN0

3.

Nitrogen pentoxide
distillation of

is

anhydrous

nitric acid

a white, crystalline solid, made by the with phosphorus pentoxide.

Nitrous acid is probably 234. Nitrous Acid. contained in a solution of nitrogen trioxide in water;

212

NITROGEN ACIDS AND OXIDES.

nitrogen trioxide is, therefore, called nitrous anhydride, just as nitrogen pentoxide is nitric anhydride.

This relation

is

shown by the equation, 2 3

N
The meaning

+H O
2

HN0

2.

of the ending ous as applied to nitrous acid


(cf.

has already been given

168).

Nitrous acid

itself

has not been made;

but

its

to distinguish them from the salts (called salts of nitric acid) are formed when a solution of nitrogen trioxide is neutralized by bases.
nitrites

Thus, potassium hydroxide and a solution of nitrogen


oxide give potassium nitrite and water, as
equations,
(1) (2)
is

tri-

shown by the

N +H KOH+HN0
2

2
2

HN0 KN0 +H 0.
2.

second

way

in

the abstraction of

which nitrites are formed oxygen from nitrates.

is

by

Thus, potassium nitrate loses one-third of its oxygen when heated to a high temperature. The equation is,
2

KN0

2
is

KN0 +0
2

2.

The temperature

required

much

lower

if

the nitrate

is

mixed with lead when heated; for the lead unites with the liberated oxygen to form lead oxide, PbO.

As was stated 235. Nitrogen Trioxide (N 2 O 3 ). in 234, nitrogen trioxide is the anhydride of nitrous

NITROGEN DIOXIDE.
acid.
It

213
nitric acid

may

be made by the action of

of specific gravity 1.3


starch.

upon

arsenic trioxide or

upon

The brown fumes


When,
oxide,

called the trioxide

may
is

be condensed by a
the real trioxide.

freezing mixture to a blue liquid,

which

however, this liquid is distilled, the

trogen trioxide, but a mixture of the dioxide

vapors are not ni(N0 2 ) with nitric

*236. Nitrogen Dioxide and Nitrogen Tetroxide

(NO 2 and

NO
2

nitrogen trioxide the proportion of


it is

a liquid;

Nitrogen dioxide lies between and nitrogen pentoxide as regards oxygen it contains. Below 22 C. but it is usually known in the form of
4 ).

its

vapor.

Nitrogen

tetr oxide ("

temperatures, but it extent even at C., into nitrogen dioxide. sociation increases as the temperature rises: -

four) exists at low dissociates readily, to some

tetra

"

Dis-

N
The degree of

^=1

N0
is

the dissociation

shown by the dark-

ening of the color, nitrogen tetroxide being colorless, but nitrogen dioxide brown.

When nitrogen tetroxide is dissolved in much cold water, the solution contains a mixture of nitrous and nitric acids; hence nitrogen tetroxide is the anhydride of both of these acids,
The equation showing
this fact
2

is,

N
*

4 (

= 2 N0 2 )+H

HN0 +HN0
2

3.

The names used

are in accordance with the latest nomenclature.

214

NITROGEN ACIDS AND OXIDES.


is

formed when most nitrates The vapors may be condensed by passing them through a U-tube surrounded by a freezing mixture. The decomposition of lead nitrate
Nitrogen tetroxide
(c/.

230) are heated.

corresponds exactly with that of nitric acid, as

is

shown by the equation, -

Pb(NO 3

)2

PbO+N O +O
2

f. (c

226).

Two other oxides of 237. Nitric Oxide (NO). nitrogen are known, viz., nitric oxide and nitrous oxide; both are colorless gases at the ordinary temperature and pressure. Nitric oxide is produced

when

nitric acid of specific

gravity 1.2 is allowed to react

with copper.
(cf.

The
is,

equation has already been given


3

227).
2

It

Cu+8 HN03

>3 Cu(N0 3 ) 2 +4

H 0+2 NO.

Nitric oxide
of
it

is slightly heavier than air. One liter under standard 1.34 conditions, grams. weighs,

The

gas

is

only slightly soluble in water.

When
FeS0 4
,

pound

nitric oxide is passed into a solution of ferrous sulphate, large quantities of the gas are absorbed, a brown comof ferrous sulphate and nitric oxide being formed. When

the solution containing this oxide escapes.

compound

is

heated, pure nitric

Nitric oxide becomes

brown when

it

comes into

contact with

air or

oxygen, owing

to the formation

of nitrogen dioxide.

NITROUS OXIDE.
One volume
The amount
piece of metallic

215

of nitric oxide consists of one-half a

volume of nitrogen and one-half a volume of oxygen.


of the nitrogen

sodium

in

may be shown by heating a a measured volume of the gas over

mercury (see Fig. 52). The sodium combines with the oxygen
of the nitric oxide, leaving the

nitrogen.

The volume of the nitrogen should be just half that of the nitric oxide taken.

supports the combustion of phos-

Nitric

oxide

FlG

52 .

phorus and of magnesium, as well as of sodium.


238. Nitrous

Oxide

(N 2 O).
heating

Nitrous

oxide

is

commonly made by

ammonium

nitrate

(NH N0
4

3)

to 170

C., or, better,

by heating a mix-

ture of sodium nitrate

and ammonium sulphate to


is

a slightly higher temperature. The formation of nitrous oxide


several reactions.

the result of
nitrate
nitric acid

At

first

the

ammonium

probably dissociates into ammonia and


just

as

ammonium

chloride

gives

ammonia and

hydrochloric acid.

The ammonia and nitric acid do not, however, recombine when cool, because the nitric acid oxidizes the hydrogen of the ammonia to
water.

The final equation for the decomposition nium nitrate is, -

of

ammo-

NH N0
4

N 0+2 H O.
2

216

NITROGEN ACIDS AND OXIDES.


this the equation for the decomposition of
(

Compare with

ammonium

nitrite

187).

Note that

all

of

the hydrogen

is

oxidized to water in each case, and that it is the oxygen in excess of that required to oxidize hydrogen that causes the formation of nitrous oxide

when ammonium

nitrate

is

decomposed.

Nitrous oxide is the only gas besides oxygen that will re-ignite a glowing splinter. The volumetric composition of nitrous oxide may be determined in the same way as that of nitric oxide,
by taking out the oxygen by means of sodium. There is, however, a great difference in results; for
viz.,

while one volume of nitric oxide contains one-half

a volume of nitrogen and one-half a volume of oxygen, one volume of nitrous oxide contains one volume of nitrogen and one-half a volume of oxygen.
Nitrous oxide
it is

may be

a commercial

article.

condensed to the liquid form; as such When the pressure under which the

gas is kept is removed, some of the liquid vaporizes, producing " " which dentists use to produce insensibility the laughing gas to pain.

Nitrous oxide
at

easily soluble; 1 volume of water C. absorbs 1.3 volumes of the gas. One liter at
is

standard conditions weighs 1.97 grams.


239. Hyponitrous Acid
i. e.j

(NOH)

2.

Hyponitrites,

for hyponitrous acid, some time, but the acid itself has only recently been isolated. A solution of hyponitrous acid decomposes
salts of

have been known

EXERCISES.
readily,

217
according
to the

giving

nitrous

oxide,

equation,

(NOH) 2
Nitrous oxide

N O+H O.
2 2

may

thus be looked upon as in some sense the

anhydride of hyponitrous acid; but the union of nitrous oxide and water to form the acid does not take place.

240. Exercises.
1
.

How many
1

from
2.

grams of nitric acid can be made, theoretically, sodium nitrate with sulphuric acid? What will be the volume of 28.4 grams of commercial
kg.

nitric acid?
3.

How much

sulphuric acid (calculated as

100%

H S0
2

4)

will

be needed to give 1,260 grams of nitric acid with potassium nitrate, if potassium hydrogen sulphate is formed? 4. Calculate the percentage composition of nitric acid?
5. How much potassium hydroxide is required to neutralize exactly a solution containing 42 grams nitric acid? 6. How could you separate a mixture of silver and gold

chemically?

450 grams lead nitrate?

grams nitrogen tetroxide could be made from How much oxygen? 8. How many grams nitric oxide can be made, theoretically, from 100 grams nitric acid with copper? How much copper is needed? How much cupric nitrate is formed? C. and 760 mm. 9. How many liters of nitrous oxide at can be made from 240 grams ammonium nitrate? How many at 20 C. and 720 mm.? 10. How would you distinguish between nitrous oxide and
7.

How many

oxygen?
11.

How many

cubic centimeters of each of


c.c.

its

constituents

combine to form 100


nitrous oxide?

nitric oxide?

To form

100

c.c.

of

218
12.

NITROGEN ACIDS AND OXIDES.


Name
three different classes of nitrates, basing the difupon the way in which the members of each class

ference

decompose when heated. 236 to a molecular equation. 13. Change the last equation in If you were to collect a given volume of the gases evolved in this reaction, what per cent, by volume, would be oxygen? Suggest how you could remove the nitrogen tetroxide, and leave
the oxygen.

CHAPTER XX.
EQUILIBRIUM AND MASS ACTION.
In Physics we 241. Equilibrium. body that is at rest as acted upon
forces.

consider

Thus, a weight held in


is

by opposing the hand is acted

upon by gravity, which and by the muscular

pulling it toward the earth, force of the arm and hand,

which opposes gravity. Neither force ceases to act, but the weight does not move,, because the two " " " in forces are or balance each
equilibrium,"

This idea of equilibrium applies to all physical and chemical changes. In physical changes, such as
other.

of physical state, we call it physical as applied to chemical reactions, it is equilibrium; called chemical equilibrium.

solution

and change

242. Physical Equilibrium, a. Between Solute and Solution. When a solute is brought in contact

much
to

with a solvent, the solute expands to fill the solvent as a gas expands into a vacuum. As soon as some solute has dissolved, dissolved particles begin
return
to

the

undissolved

state.

These two

opposing operations go on
is,

until they are equal, that

until as many molecules separate from solution in a given tune as dissolve in the same time. The
219

220

EQUILIBRIUM AND MASS ACTION.


is

then one of physical equilibrium between dissolved and undissolved solute.


condition in the solution
It is expressed

by the

equilibrium equation.
* (

Solute (undissolved)

Solute (dissolved).

The double arrow


84).

is

this condition of equilibrium exists the solution

read -"is in equilibrium with." When is saturated (cf.

Solution and separation from solution continue, for the

energy of the molecules remains, but if the temperature and pressure remain constant, the solution becomes neither more
concentrated nor more dilute.
is set

// we change the conditions slightly,

up for the new conditions. Thus if however, equilibrium we have undissolved potassium nitrate in equilibrium with its saturated solution at 20 C., and raise the temperature to 25 C.,
potassium nitrate
there
is

dissolves

until

equilibrium at the higher

temperature.

its

Between a Liquid and Vapor. If a vessel of air be inverted over water (cf.
(6)

Fig.

53),

two physical equi:

libria are
(1)

soon set up The molecules of water


surface (as

leave the water

steam) and enter the air layer; at the same time molecules of steam return to the water. When the two actions are equal, there is equilibrium :

Water

(liquid)

Water
"

(gaseous).

The

air is

then

"

saturated

with water vapor.

CHEMICAL EQUILIBRIUM.
(2)

221

The molecules

of air,

i. e.,

of its constituents,

enter the water,

and dissolved
*
~<

air leaves the water,

until the

two actions are equal.


Air (undissolved) Air (dissolved).
air.

The water

is

then "saturated" with

In case

(1), as in the case of the potassium nitrate, a change in conditions alters the point at which equilibrium
is

reached.

If

the temperature

is

raised,

more water

will

change to steam to produce saturation. If the air layer be in motion, as when water stands in an
is

open dish, equilibrium water " evaporates."


243. Chemical

never reached; hence, the

Equilibrium.

Just

have two opposite physical changes balancing each other, so there may be two chemical reactions which, if carried to completion, would give exactly
opposite results.
following
(1)
(cf.

as "

we may
"

Two
:

reactions so related are the

213)

Nitrogen and hydrogen unite, under the

in-

fluence of the electric discharge, to give

ammonia. conAmmonia is under the same (2) decomposed, and ditions, giving nitrogen hydrogen. Each of the reactions is reversible, and both may be represented by the equilibrium equation, -

N +3 H
2

NH

3.

The reason

for the reversibility

is

that

all

the sub-

stances concerned are gaseous, and, therefore, re-

222

EQUILIBRIUM AND MASS ACTION.

main subject to the action of the electric discharge. The conditions are, thus, similar to those existing

when

physical equilibrium

results:

nothing

is

re-

moved from

If any one of the the sphere of action. three substances is removed, the reaction will go to

completion.

The equilibrium between steam, hydrogen, and oxygen


(" dissociation of

steam

") at high

temperatures

is

another case

of the

same

sort

(cf.

73).

For a third case we have the two reversible reactions given " " 56 and 57) Hydrogen (cf. (1) When steam is passed over heated iron the products are magnetic iron oxide and hydrogen.
under
:

(2) When hydrogen is passed over the heated iron oxide, the products are steam and iron. The equation for both is the equilibrium equation,

3
If

Fe+4

Fe 3

+4 H

2.

steam acted upon


is

iron, or

closed tube, this condition of equilibrium

hydrogen upon iron oxide, in a would be reached. But


is

when steam

passed over iron, the hydrogen produced

carried

away by the steam, and the reaction, as read from left to right, In the same way, the reverse action becomes is a complete one.
complete
if

the steam formed

is

removed by the hydrogen.

Under " ionization " we 244. Ionic Equilibrium. learned that for ordinary concentrations ionization
is

incomplete.
is

Thus normal hydrochloric


dissociated at 18

acid
is

(cf.

178) 78.4% dissociation incomplete?

C.

Why
is

the

The answer

that while

the solvent permits (or causes) the dissociation, the

CHEMICAL EQUILIBRIUM IN SOLUTION.

223

oppositely charged ions unite, in part, to form the

molecular ionogen.

HCl;=H+Cl.
Here, again, equilibrium
is

reached.

Raising the
increase

temperature

and

diluting

the

solution

the ionization; lowering the temperature and concentrating the solution cause the ions to recombine.
245. Chemical Equilibrium in Solution.
actions, in solution, of the type,

All re-

AB+CD

AD+BC,

are reversible, unless either Thus, the reaction represented

AD or BC
+KN0

is

insoluble.

by the equation,
3,

AgN0 +KCl
3

AgCl |

is

practically complete, because of the slight solu179), but the reaction, bility of silver chloride (cf.

Pb(N0 3 2 +2 KC1
)

PbCl 2

+2 KNO

3,

is

much
The

less

complete, because lead chloride


(cf.

is

more

soluble than silver chloride

Appendix,

viii).

reactions for the preparation of nitric acid


(cf.

and hydrogen

chloride are true reversible reactions

225), but they become practically complete because the acids are removed in gaseous

form.

Thus,

NaCl+H 2SO4

NaHS0 +HCl T
4

224

EQUILIBRIUM AND MASS ACTION.

The reversibility of this reaction may be shown by mixing concentrated solutions of sodium hydrogen sulphate and hydrochloric acid.

Sodium

chloride
2
4

is

precipitated.

NaCl

+H S0
:

<

NaHS0 +HCl.
4

In more dilute solutions,


there
is

all

the substances are soluble, and

equilibrium

NaCl+H S0 ;=
2 4

NaHS0 +HCl.
4

In
ucts

all

reactions
is

the cases considered, double decomposition become complete because one of the prodin

removed
is

an insoluble form. In neutralizathe completeness of


the

tion this

not the case:

reaction depends, rather, on the fact that water is only very slightly dissociated. Yet, slight as is the
ionization represented

by the equation,

H
it is

^= H+OH,

salts

sufficient to produce hydrolysis (cf. 184) of formed from any but the strong acids and bases.

246.

Mass

Action. - -

The combination

of particles

(molecules or ions), whether in gaseous form or in solution, is .influenced by the frequency with which

the particles meet. If, therefore, we wish to stop or to diminish the dissociation of a substance AB,

we

duced

Jby the dissociation, thus increasing the active

that an excess of one of the particles proe. g., A, is present. By mass of A, we diminish the possibility that B can exist uncombined with A.
see to
it

EXERCISES.

225

The

action of an excess of one of the substances

(or ions)

produced in a reversible reaction

is

called

Mass
PC1 5
,

Action.
the molecular weight of phosphorus pentachloride, by vapor density methods, is too low, owing

To illustrate:

as determined

to the dissociation of
trichloride

some

of the molecules into phosphorus

and

chlorine.

PC1 5

^=

PC1 3 +C1 2

The
ride;

mination

dissociation can be prevented if the vapor density deteris carried out in an atmosphere of phosphorus trichlo-

because the chlorine molecules then meet molecules of

phosphorus trichloride so frequently that practically no chlorine molecules remain free. Similar effects occur in solution. Thus, if we wish to precipitate the sulphuric acid, i. e. the SO* ions, contained in a
t

solution,

we use barium chloride solution. If we use exactly the theoretical amount of barium chloride, however, much barium The reaction sulphate remains in solution (as Ba and S0 4 ions)
.

is

only partly represented by the equation,

Ba+2 Cl+2 H+SO

BaS0 4 + 2

H+2 Cl,

for the reverse operation also goes on.

BaS0
Whatever
will

Ba+S0

4.

cause the SO* ions to meet more

Ba

ions in a

given time will increase the precipitation of the /S0 4 ions as barium sulphate. We obtain this result by adding a large excess
of

barium chloride solution.

247. Exercises.
" a does the amount of steam necessary to "saturate given volume of air (cf. Fig. 53) compare with the amount that
i.

How

-226

EQUILIBRIUM AND MASS ACTION.

would evaporate into this space if air were not present; that is, " vacuum "? if the space were a 2. Write the equation showing the equilibrium between water C. C. and some ice floating in it, if the room is also at at were room of the if What change would occur the temperature
raised slightly?
in 3. Write the equation for the equilibrium between salt contact with a saturated salt solution. What result would follow
if

water were added? added? Why?

If

concentrated hydrochloric acid were

4. To precipitate all the manganese of solution as the sulphide, (cf. 256),

manganous sulphate

MnS

we

use an excess of

sodium sulphide. Why? 5. Write the equation for the equilibrium between ammonium hydroxide and its ions. For the equilibrium between ammonium If a concentrated solution of ammonium chloride and its ions. chloride were added to ammonium hydroxide, would the mixture
be as strong a base as the

ammonium

hydroxide alone?

Why?

CHAPTER
SULPHUR AND
ITS

XXI.

COMPOUNDS.

248. Occurrence and Preparation of Sulphur. Sulphur occurs in nature in both a free and a combined form.
chiefly

In the free condition


Sicily,

it

is

obtained

from

Louisiana.

with
rial,

much

Mexico, and, to some extent, from Natural sulphur is usually found mixed earthy mateit

from which

must

be separated to prepare it for the market.

The

first

operation in
sul-

the purification of

phur usually

consists in

heating the natural product; the sulphur melts

and flows away, leaving


the
infusible

impurities

behind.

In the second operation the partially purified sul-

phur is distilled from large iron retorts (see Fig. 54), and is thus separated from less volatile impurities.
The melted sulphur in the reservoir A is allowed to flow from time to time into the retort B, in which the sulphur is vaporized.
227

228

SULPHUR AND ITS COMPOUNDS.


passes into the condenser collects either bottom (C) of the condenser, or in a

The sulphur vapor which


solid state

in the liquid state, at the

(D). The liquid sulphur is run thus producing the " roll-sulphur," or " brimstone of commerce; the sulphur which solidifies upon the walls appears in the form of fine meal and is called " flowers "

upon the cold walls


crystallize,

into "

molds to

(more correctly,

"

flour ") of sulphur.

like

249. Physical Properties; Allotropism. Sulphur, many other elements, exists in several different
of sulphur

physical forms;
ties

phur

to

we must which we are

consequently, in giving the properspecify the kind of sul-

The several referring. varieties of sulphur may be


grouped into three classes
(1)
:

FIG.

55.

(c /-

Ordinary, or rhombic, Fi S- 55 and Appendix, xi).

sulphur This is

to

it

less,

the natural form. All other forms revert It is yellow, odorless, tasteat the ordinary temperature. melts at 114.5C., has a specific gravity of 2.06, and is

46 g. in 100 g. of CS 2 at the very soluble in carbon disulphide ordinary temperature. In water it is insoluble. Roll sulphur is rhombic; so are the crystals that separate

from carbon disulphide solution.


(2)

(Fig. 56).

prismatic, or monodinic, sulphur This is formed by slow cooling

of melted sulphur.

As soon

as a crust

forms,
is

it is

broken, and the liquid sulphur


off.

poured

The

crystals are long,

FIG.

56.

almost colorless needles, that melt at 119 Their C., and dissolve in carbon disulphide.
1.96.
If

specific gravity is

kept below 96 C., they change, in a few days, to the

CHEMICAL PROPERTIES.

229

rhombic form, with evolution of heat. On the other hand, rhombic sulphur changes to prismatic above 96 C.
(3) Amorphous, i. e., non-crystalline, sulphur. Ordinary sulphur behaves peculiarly when heated. At 114.5 C. it becomes a yellow liquid. Above 160 C. it is dark and viscous, and at 230 it can hardly be poured. Above 300 C. it is limpid again, and at 445 it boils, giving a light-brown vapor. If it is allowed

to cool slowly, these changes are repeated, in the reverse order, and ordinary sulphur is finally obtained. If, however, boiling

sulphur

is
is

chilled suddenly, as

by pouring

it

into cold water, the

an elastic, non-crystallized substance. After several product days this becomes hard, and consists partly of rhombic sulphur, which is soluble in CS 2 and partly of an amorphous variety, which is insoluble in CS 2 Amorphous sulphur is the hardened form of the dark, viscous liquid. Because of the sudden cooling, it was not given time to change into the ordinary form. When it is kept below 96, it changes slowly into rhombic sulphur with evolution of heat. At the ordinary temperature the change
,
.

may
"

take years.

Flowers of sulphur

"

have a nucleus of rhombic

crystals

and

an amorphous covering.
sical

The existence of an element in several phyAllotropism. forms is called allotropism, and the different varieties are
Allotropism

called allotropic forms of the element.

may

be due

to different arrangements of the atoms in the molecule, to different numbers of atoms in the molecule, or to other causes. In the

change of one form into another, an energy-change observed (c/. 312).

is

usually

Sulphur unites diProperties. with rectly many elements, especially with metals. Thus, when a mixture of powdered iron and sulphur is heated, or moistened with water, or strongly
compressed,
it

250. Chemical

unites chemically, forming

ferrous

230

SULPHUR AND ITS COMPOUNDS.


Similarly, copper foil burns in sulphur

sulphide, FeS.

vapor, giving cuprous sulphide. Mercury combines with sulphur when the two are simply triturated,
i.

e.,

rubbed together

in a mortar.

illustrations of the action of sulphur Thus, silver egg-spoons are blackened by the sulphur contained in eggs; and silver coins which have been carried about in the pockets are colored by the sulphur of the

There are

many common

upon metals.

perspiration.

The illuminating gas of many cities contains sulphur compounds; this fact accounts for the tarnishing of articles of brass, copper, lead, silver, etc., in houses in which such gas is used.

At about 260 C. sulphur begins to unite with the If sulphur at a temperature oxygen of the air. below 260 C. is examined in the dark it will slightly be found to phosphoresce, i. e., glow. In burning, sulphur produces sulphur dioxide, SCV This is an invisible gas having the characteristic odor of burning sulphur.
.

251.

Uses

of Sulphur.

preparation of
rubber goods

many

Sulphur is used in the important substances. Thus,

vulcanite are made by heating toand sulphur; match tips, especially caoutchouc gether the older forms, contain sulphur as an ingredient; gunpowder, as previously stated, is a mixture of

and

charcoal, sulphur, and niter; and sulphur dioxide, which is used for bleaching and as a germicide, is made by burning sulphur in air.

COMPOUNDS OF SULPHUR.
Finally,

231

used in the preparation of sulphuric acid, which is possibly the most important substance manufactured.
sulphur
is

Sulphur 252. Compounds of Sulphur. stituent of many important compounds;

is

a con-

for the

sulphides, next to the oxides, are the most common ores of the metals. Among the natural sulphides

are iron pyrites (FeS2 ), galena (PbS),

sulphide (H 2 S). conditions.

The

latter is

and hydrogen a gas under ordinary

The two important


dioxide

oxides of sulphur are sulphur

and sulphur trioxide. With hydrogen and oxygen sulphur forms sulphuric acid and other acids, and with metals and
oxygen, sulphates, sulphites, thiosulphates, etc. The most important natural sulphate is gypsum, CaS0 4 2 2 0. Natural barium sulphate, BaS0 4
.

is

called

"

heavy spar."
,

Both are important minerals.

Iron pyrites, FeS 2


dioxide.

is

When

it is roasted,

a source of both sulphur and sulphur i. e., heated in a current of air, its
,

sulphur is oxidized to sulphur dioxide, S0 2 but if the iron pyrites is heated without access of air it breaks down into a compound of iron and sulphur containing only two-thirds of the sulphur of
the original pyrites.

The equation

The excess of sulphur is liberated. representing this reaction is,


3

FeS 2

Fe 3 S 4 +2

S.

The

reaction

is

like that
(c/.

dioxide is heated

22),

which takes place when manganese and which is indicated by the equation,

Mn0

Mn

+0

2.

232
253.

SULPHUR AND ITS COMPOUNDS.

Hydrogen Sulphide. Hydrogen sulphide a colorless gas formed by the decomposition of It has the organic substances containing sulphur. odor of rotten eggs. So-called " sulphur " waters
is

contain

it.

Its

specific
is

gravity

is

1.18

(air

= l).

Hydrogen sulphide
sulphide.

usually prepared

of dilute hydrochloric or sulphuric acid

by the action upon ferrous

FeS+2 HC1

FeCl 2
is

+H S
2

Hydrogen sulphide
its

decomposed by heat into

burns completely to water and sulphur dioxide, but when the supply of air is limited, as in the burning of a bottle of the gas, the hydrogen burns, but some of the sulphur does
elements.
jet of the gas

not.

3 volumes of the gas.

Under standard conditions one volume of water absorbs The solution is a weak acid hydro sulacid.
Its

phuric

ionization

is

expressed

by the double

equilibrium equation,

H S ^= H+SH ;=
2

+
2

H+S.
consider
its

In writing equations containing

H S,
2

we

ions to be

+
2 H+s".

light

The aqueous solution is easily decomposed, especially in the and when warm, by the oxygen of the air; hence it soon
and deposits sulphur.
2

loses its odor,

H S+O
2

>

H 0+2 S 1
2

SULPHIDES.

233

Chlorine and iodine react with hydrogen sulphide solution in a


similar

way:

H S+C1 H S+2 I
2 2

HC1+S I HI+S |
.

The gas and its solution react with most metals, giving sulphides and hydrogen:

Fe+H S
2

FeS+H

T.

Hydrogen sulphide
Thus,
it

is, as we might expect, a reducing agent. reduces concentrated sulphuric acid to sulphurous acid

(c/.265):-

H S0 +H S
2 4
2

>

H S0 +H 0+S j
2

The salts of hydrosulphuric 254. Sulphides. acid are the sulphides. They are formed in several
ways:
(1)

--

(2)

By the union of metals with sulphur. By the action of metals with hydrogen
By By

sul-

phide.
(3)
(4)

the reduction of a sulphate or sulphite. the reaction between a base and hydro-

sulphuric acid. (5) By the reaction between hydrogen sulphide, or some other soluble sulphide, and soluble salts of

some metals.
An
illustration of the third

method

is

the reduction of sodium

sulphate,

when heated with

charcoal, to

sodium sulphide:
T
.

Na2SO,+4 C
An
illustration of the fourth

NaoS+4 CO
method
is

the absorption of
:

hydrogen sulphide by sodium hydroxide solution


2

NaOH+H S
2

>

Na S+2
2

H,>O.

234

SULPHUR AND ITS COMPOUNDS.

If we pass hydrogen sulphide into sodium Hydrosulphides. hydroxide solution as long as it is absorbed, we get sodium

hydrosulphide,

NaSH:-

NaOH+H S
2

>

NaSH+H 0.
2

This forms a solution neutral to litmus.


the

If,

NaSH

as

much NaOH

as

was used

originally,

now, we add to we obtain an

alkaline solution containing

Na2S

in equilibrium with

NaSH and

NaOH:

NaSH+NaOH ^= Na S+H 0.
2 2

Evaporation of the solution gives crystalline Na2S. Amsulphide, (NH 4 ) 2S, is prepared (in solution) hi a similar way.

monium

255. Precipitation

of

Sulphides.
i. e.,

The

fifth

method
of

of

forming a sulphide,

by

the addition

a soluble sulphide to the salt of a metal, will succeed only if the sulphide desired is insoluble in

the solvent used. Thus, hydrogen sulphide reacts with cupric sulphate solution to give cupric sulphide (a black precipitate) and sulphuric aci'd
:

(1)
(2)

CuS04 +H 2S

CuS

+H S0
2

or,
4.

Cu+SO +2 H+S~
4

CuS |

+ H+S0
2

Since CuS is very insoluble, both in water and in dilute acids, all the ionic copper of the solution may

be removed by

H S,
2

i. e.,

by

S:

++

Cu+S

CuS 1

PRECIPITATION OF SULPHIDES.

235

But no

result follows

when

HS
2

is

added to sodium

sulphate, because

all of

the products are soluble:

Another fact must be considered in

this connection:

many

sulphides that are not precipitated by hydrogen sulphide are precipitated by a metal sulphide, e. g., Na2 S.

This

is

the case with manganous sulphide,


(3)

MnS
2

MnSO +Na S 4
2

>

MnS | +Na S0

4.

The equilibrium
(4)

reaction represented
4

MnS0

+H S ~
2

- MnS+H

by the equation,
2

S0 4

is forced backward, giving hydrogen sulphide, rather than forward, to give manganous sulphide, owing to the action of the No MnS is sulphuric acid upon the manganous sulphide.

We ought to expect this, since 2S is commonly prepared from a sulphide (FeS) by the action of an acid (cf. 253). The difference between the reactions of equations (3) and (4) is
precipitated.

due to the

fact that

MnS,

in spite of its

apparent insolubility

[equation (3)], is still appreciably soluble in water. That is to say, the change expressed by the physical equilibrium equation
(cf.

242),-

MnS
ionized,

(solid) 7

- MnS

(dissolved),

goes forward to an appreciable extent.

The

dissolved

MnS

is

MnS 7

- Mn+s7
H, hence the reverse action

and the sulphuric acid, i. e., H, reacts with S, giving H 2S. Hence H2S escapes from the solution as rapidly as it is added. The

Na2S

[equation

(3)j

gives S, but not

236
is

SULPHUR AND

ITS COMPOUNDS.
is precipitated.

not appreciable, and

MnS

The

solubility of

.CuS [equations (1) and (2)] is so small that the reverse action due to the 2 S0 4 is insignificant.

The sulphides of the metals are thus divided into three groups (1) The soluble sulphides, such as Na 2 S, BaS, etc. These
:

are not precipitated, either


(2)

by H 2 S or by a metal sulphide. The very insoluble sulphides, such as Ag2 S, PbS, CuS, and As 2 S 3 These are precipitated by H 2 S, even if a dilute acid is
.

present.

ZnS,

sulphides, such as FeS, MnS, These are not precipitated by H?S, or only slightly (not at all if acid is added), but are precipitated by a metal sulphide, such as Na 2S and (NH^S. These facts form the basis of that branch of Chemistry called qualitative analysis, for they enable us to classify all the com(3)

The moderately insoluble

etc.

mon

metals into three groups.

Carbon disulCarbon Bisulphide (CS 2 ). of carbon and formed the direct union by phide old method to The was pass sulphur vapor sulphur. in the modern method an electric over hot charcoal furnace is used to bring about the reaction. Pure carbon disulphide is colorless, and has an ethereal
256.
is
;

odor; but as obtained commercially it is often yellow, and has a disagreeable smell. The liquid boils at 47 C., and has a specific gravity of 1.27. It is very
inflammable.

CS 2 +30 2
The

C0 +2S0
2

2.

chief use of carbon disulphide

is

caoutchouc, phosphorus, iodine, resins


insecticide. Carbon ietrachloride,

and waxes.
(cf.

as a solvent for sulphur, It is also an


533), used as

CC1 4

a non-

SULPHUR DIOXIDE.
inflammable cleaning agent for fabrics,
disulphide:
.

237
made from carbon

is

CS +3
2

C1 2

CC14 +S 2 C1 2

Sulphur dioxide is the well-known odor produced by burning sulphur in air or oxygen. Commercially it is usually formed by roasting a sulphide, e. g., iron pyrites (cf. 252).
gas of
4 FeSa+11
2

257. Sulphur Dioxide.

FeaQs+S S0 2

Sulphur dioxide is formed by the spontaneous decomposition of sulphurous add, H 2 SO 3 When, therefore, this acid is formed in a double decomposition, as when a sulphite is treated with a strong acid,
.

sulphur dioxide results.

Na S0 +2 HC1
2 3

H S0 +2 NaCl.
2

H S0
2

H 0+S0
2

The common laboratory method centrated sulphuric acid with copper.

is

to heat con-

Cu+2 H S0
2

CuS0 4 +2

H 0+S0
2

2 T

stages of the reaction are given in 265. Sulis colorless, and 2.2 times as heavy as dioxide phur 80 c.c. in 1 c.c. air. It is very soluble in water

The

water at
is

C.

The gas is

expelled

when

the solution

heated.

238

SULPHUR AND ITS COMPOUNDS.

passing

Sulphur dioxide may. be obtained in liquid form (Fig. 57) by it through a condensing tube (conveniently in U form) surrounded by a freezing mixture of ice and salt. The resulting
liquid 8 at
is

colorless;

it

boils

C.

The evaporation

of liquid sulphur dioxide absorbs much heat; hence this

substance

is

often used as a

refrigerating agent.

ties of

258. Chemical ProperSulphur Dioxide.


of the chemical

-Most
H 2 SO 4

properties of sulphur dioxide are those of its ICE AND NaOH SALT solution, which contains

FIG. 57.

sulphurous acid ( 259). This is oxidized slowly by the air to sulphuric acid. With oxidizing agents the change is rapid. With nitric acid and with chlorine water the equations

are:3 H S0 +2 HN0 H S0 +C1 + H


2 3 2 3 2 2 3

H S0 +H + 2 NO. H S0 +2 HC1.
3
2

etc.,

Solutions of potassium chromate, bichromate, permanganate, are all reduced by sulphur dioxide. Sulphur dioxide oxidizes

hydrogen sulphide:
2

H S+S0
2

H 0+3 S 1
2

Natural deposits of sulphur may be formed in this way, as both gases are evolved in volcanic action.

The

chief use of sulphur dioxide, aside


is

from

its

being the source of sulphuric acid,

as a bleaching

SULPHUROUS ACID.
agent of silks, woolens, straws, would be injured by chlorine (cf.
The sulphur
of these fabrics, forming colorless

239
etc.,

laces,

which

122).

dioxide probably unites with the coloring matter

compounds. The bleaching a time, however; hence fabrics bleached " " with age. Dilute sulphuric acid, also, by sulphur yellow restores the color of many articles that have been bleached by
effect disappears after

sulphur dioxide; it probably breaks up the colorless compounds that were formed.

Sulphur dioxide

is

used also as a disinfectant.

solution of sulphur 259. Sulphurous Acid. dioxide in water has the properties of a weak acid, and is called sulphurous acid, 2 S0 3 Sulphur dioxide

is, therefore, sulphurous anhydride. has not been isolated (cf. 211).

The

free acid

When

sulphurous acid

is

neutralized

by the

solu-

and the solution is evaporated, a is obtained. The same result follows when sulsulphite dioxide is phur gas passed into the solution of an alkali.
tion of a base,

As in the case of sulphuric acid, two sets of salts exist. Thus, an exactly sufficient amount of sulphur dioxide is used with sodium hydroxide, the product is sodium sulphite, Na 2 S0 3
if
.

The equation
2

is,
2

NaOH+H S0

Na S0
2

3 -f-2

H 0.
2

If, however, sulphur dioxide is passed into sodium hydroxide solution until no more gas is absorbed, the solution contains

sodium hydrogen

sulphite,

NaHS0

3.

The equation
2

is,

NaaSOa+HaSOs

NaHS0

Similar reactions take place with other bases.

240

SULPHUR AND ITS COMPOUNDS.


sulphites are decomposed and by hydrochloric acid,

Both normal and acid


dilute sulphuric acid giving sulphur dioxide.

by

Na S0 +2 HC1 NaHSOa+HCl
2
3

>

NaCl+H2S0 3 (i. e., S0 2 +H 20). NaCl+HjSO. (i. e., S0 +H 20).


2

By

this reaction a sulphite

may

readily be distin-

guished from a sulphate.


Sulphites, like sulphurous acid, oxidize readily in the air.

260. Sulphur
colorless

Trioxide.

liquid above 15

Sulphur trioxide is a C., its melting point.

Below

boils at

The liquid it is a white, crystalline solid. 46, and is changed by a trace of water to a the form in compact mass of fibrous crystals
this
.

In the air, sulphur trioxide gives off dense, choking fumes. It reacts with water, producing a hissing noise and much

which the substance

is

usually known.

heat.

Sulphur trioxide 161):-

is

sulphuric anhydride

(cf.

H 0+S0
2

H S0
2

4.

It also

combines with the oxides of metals

CaO+S0
giving pyrosulphuric acid,
sulphuric, and disulphuric

CaS0 4

Concentrated sulphuric acid combines with sulphur trioxide, This is also called fuming 2 S 2 C>7.

acid.
is

Preparation.

Sulphur trioxide

of sulphur dioxide.

small

amount

produced by the oxidation is formed when sulphur

CONTACT PROCESS.

241

burns in air or oxygen. The union of sulphur dioxide and oxygen incomplete, when the two are heated together, because the reverse action takes place:
is

SO

+0

2S0

3.

When

combination

a catalyzer, such as platinized asbestos, is used, the is made almost complete. The tube containing the

S024Air

platinized Asbestos

FIG. 58.

are-

is heated to about 360 C., and the dry gases it. The sulphur trioxide may be collected through passed in a cooled receiver, or it may be absorbed by concentrated

catalyzer (Fig. 58)

sulphuric acid. Platinized asbestos is made by soaking fibrous asbestos in chlorplatinic acid, and then decomposing the plati-

num compound by
vanadium oxide and

heat

(cf.

517).

ferric oxide, are

Other catalyzers, such as sometimes used.

"

261. Contact Process for Sulphuric Acid. --The " is the more modern of the two Contact process
of
.

making sulphuric acid. It making sulphur trioxide consists, essentially, The older ( 260), and then treating it with water. " " Chamber " English," or process is called the
in

common methods

This consists in oxidizing sulphur 'dioxide process. in the presence of water (cf. 262).

242

SULPHUR AND ITS COMPOUNDS.


in the contact process
is

The apparatus used


in Fig.
59.

shown

in outline

blower," which furnishes ah* to the "burner" (B), and to the gas "mixer" and "heater" (#). In B the sulphur compound (commonly, iron pyrites) is oxidized " " to sulphur dioxide. This gas is purified by the scrubbers
is

the

"

C and
acid,

respectively.

D, containing dry coke and coke wet with sulphuric Arsenic, which is usually present in the
is

pyrites,
cessful,

and which must be removed to make the process sucremoved in the "arsenic purifier" (E). In H the

FIG. 59.

sulphur dioxide

is

mixed with
is

air,

and the mixture


is

is

heated.

The amount
246)

of air used

such that there


"

oxygen, in order that the

mass action "

large excess of

of

the

oxygen

(cf.

may make

possible. The (G), in which

the change to sulphur trioxide as complete as " heated gases then pass to the contact chamber "

combination

is

effected.

The

resulting sulphur

trioxide
acid.

is

absorbed in concentrated
trioxide

The

97-98%) sulphuric unites with the small amount of water


(i. e.,

present to give the acid. The acid centration by the addition of water.

is

kept at the required con-

262.

Chamber

Process.

In the Chamber process

sulphur dioxide, produced from pyrites or crude sulphur, is conducted into large boxes lined with " leaden chambers." Air and lead, and called the

CHAMBER

PROCESS.

243

steam are also forced in, and nitric acid is introduced from time to time. Dilute sulphuric acid is the result.
The nitric acid introduced into the leaden Explanation. a small amount of is reduced to nitric oxide, NO;

chambers

sulphur dioxide is thus oxidized directly by nitric acid. But the greater portion of the oxygen used comes from the air; for

Cu + HNO.

FIG. 60.

the nitric oxide takes


dioxide
dioxide.
(cf.

237),

All of
:

up the oxygen of 'the air, forming nitrogen and then gives up the oxygen to the sulphur these facts are represented by the following

equations

(1) (2) (3)

S0 +2
2 2

HN0 N0 +S0 +H
3 2
2

2NO+0

H S0 + 2 N0 H S0 +NO. 2N0
2

2.

2.

(4)

Repetition of

(2).

Theoretically, a very small amount of nitric acid ought to be able to oxidize an indefinitely large

244

SULPHUR AND ITS COMPOUNDS.

of sulphur dioxide, but in practice some of the nitrogen oxides are lost; hence, nitric acid must be added from time to time to the mixture in the

amount

leaden chambers.
oxides
is

The greater portion of the nitrogen prevented irom escaping by being made to

pass through towers of concentrated sulphuric acid, which absorbs them. They are then returned to the

leaden

chambers to perform again the work

of

oxidizing sulphur dioxide.

The equations given above are only incomplete representations of the reactions taking place in the leaden chambers. It is probable that the nitric oxide reacts with the steam, oxygen and sulphur dioxide present in the leaden chambers,
giving a substance called nitrosyl sulphuric acid.

is,

The equation
.

S0 2 +2
"

NO+3 0+H
is

NO. HS0 4
It

The

nitrosyl sulphuric acid

a solid substance.

is

known

chamber crystals." It is readily decomposed technically as by the excess of steam, giving sulphuric acid and nitrogen trioxide (N 2 3 ), as is shown by the equation,
2

NO. HS0 4 +H 2

H SO +N
2 4

3.

Apparatus

acid manufacture

for demonstrating the nitrosyl sulphuric is shown in Fig. 60.

The sul263. Purification of Sulphuric Acid. phuric acid obtained in the leaden chambers contains about 35% of water; it is, therefore, concentrated

by evaporation.

The evaporation
is

is

carried

out in leaden

pans until the acid

concentrated

PROPERTIES.

245
this is the case,

enough

to attack the lead.

When

further evaporation is carried out in cast-iron pans until an acid containing about 13% of water is " " crude This is the obtained. sulphuric acid of

commerce.

It

is

very impure.

If the acid is to

be

concentrated

further, the evaporation must be carried out in vessels of glass, porcelain, or platinum.
still

The pure

acid

is

made by distilling

of platinum lined with gold.

There

the crude product in stills is thus obtained an oil

gravity

boiling at 338 C. and containing only 1.5% water. Its specific is 1.854 at C. The anhydrous acid (approximately

100%

sulphuric acid)

is

made Only

in very small

amounts.

264. Properties.
colorless
liquid.

Sulphuric acid

is

a thick,

oily,

When

it

is

much heat is evolved, so much, sometimes boils. To avoid spattering of the hot liquid we pour the concentrated acid in a small stream
into the water,

diluted with water, indeed, that the water

not the water into the acid.

Sulphuric acid forms several hydrates with water, the two most important being those represented by 2 2 O. Bethe formulas, and 2 SO 4 2O 2 SO 4

cause of the tendency of sulphuric acid to take up water, it is used as a drying agent.

The dehydrating power of sulphuric acid also accounts for the fact that organic matter, e. g., paper, wood, dust, sugar, etc., are charred by it. These bodies are compounds containing
carbon, hydrogen, and oxygen oxygen are abstracted, as water,
(cf.

543).
acid,

by the

The hydrogen and and charcoal is left.

246

SULPHUR AND ITS COMPOUNDS.


of

265. Reduction acid decomposes,

Sulphuric

Acid.

Sulphuric

when

sufficiently

heated,

much

as nitric acid does; the products are chiefly sulphur dioxide, oxygen, and water. The equation,

H S0
2

- H 0+S0
2

+0,

thus represents what takes place. If we have at hand a substance that can combine with oxygen,
the decomposition of the acid takes place very easily.

The reducing agents may be


copper, mercury, etc.

sulphur,

charcoal,

The
acid,

acid has
it is

no action upon these substances


is

in the cold;

but when
i. e.,

heated with them the acid

reduced to sulphurous

to sulphur dioxide and water.

The reducing agents


is,

are, of course, oxidized.

For the action of sulphur, the equation


2

H S0 +S
2

H S0 +S0
2
3

2 (i. e.,

SQ 2 +2

H 0).
2

With copper, the partial equations


(1)
(2) (3)

H S0 +Cu H S0 +(CuO)
4 2 4

(H 2 S0 3 )

The complete equation


2

H S0 +
2 4

Cu

-- T+H are,
(

CuS0 4 +H 20;
2

S0 2

0.

is,

CuS0 4

+2H

+
2

S0

With

zinc, the reduction


is

is

carried to

hydrogen sulphide,

if

the layer of acid the hot acid (cf.

very thin, so that the

HS

is

not oxidized by

253).

SULPHATES.
(1)

247

(2)

H S+(4 ZnO). H S0 +4 Zn 4 ZnSO +4 H 0. H S0 +(4 ZnO)


2

Hence, the complete equation


5 H S0 +4
2 4

is,

Zn

H S T +4 ZnS0 +4 H 0.
2

266.
is

Uses

of

Sulphuric Acid.

Sulphuric
It is

acid
acid

in enormous quantities. preparation of nitroglycerine (

made

used in the
nitric

232),

(223), hydrochloric acid


ucts
refine

126),
It

and
is

coal-tar prod-

(232,
(

524,
(

and

petroleum

541). 525), to

also

used

to

change

starch

into

sodium carbonate by the glucose " Le Blanc process (414), and to convert the calcium phosphate of bone ash and of phosphate rocks into soluble form for use as fertilizers ( 358).
545), to prepare "

progress of civilization is proportional to the quantity of sulphuric acid used/'

"

The

As sulphuric acid is dibasic The ( 166), it forms both normal and acid salts. normal salts are formed by neutralizing basic hydroxides with dilute sulphuric acid, and by treating the oxides and carbonates of metals, or the metals them267. Sulphates.
selves,

with dilute sulphuric acid.


2

2 NaOH+H S04 ZnC0 3 +H 2 S0 4

Na2S04 +2 H 2O. ZnSO 4 +H 2 CO 3 (i. e. C0 2 T


t

+H 0).
2

Mg+H S0
2

MgS0 +H
4

Acid sulphates (also called bisulphates) are obtained when concentrated sulphuric acid reacts with sodium chloride, sodium

248
nitrate,

SULPHUR AND ITS COMPOUNDS.

acetic acids, respectively (cf. phates are also formed when

and sodium acetate to produce hydrochloric, nitric, and 126, 223, and 535). Acid sulone equivalent weight of a metal hydroxide (e. g., NaOH) reacts with two equivalent weights
of the acid:

NaOH+H S0
2

NaHS0

+H 0.
2

They are, therefore, formed from many normal sulphates and an excess of sulphuric acid. Thus, when a solution of sodium
sulphate is treated with dilute sulphuric acid, the acid sulphate is obtained (cf. 259)
:

Na S04 +H 2 S0 4
2

NaHS0

4.

Barium sulphate and lead sulphate, which are insoluble in " " dissolved water, are by hot, concentrated sulphuric acid, as

add sulphates,

BaS0 4 +H S0 4 PbS0 4 +H 2 S0 4
2

BaHS04 PbHS04

When

the solutions are treated with water, the normal sulCf. also

phates are preciptated.

88.

Stability of Sulphates.
heat, giving metal oxides,

Many sulphates arc decomposed by


and

either sulphur trioxide or its decomposition products, sulphur dioxide and oxygen (cf. 222).

Fe 2 (S0 4 ) 3

CuS0 4
The
phates when heated
2
:

Fe +3 S0 CuO+S0 T.
2

T.

acid sulphates of sodium and potassium give pyrosul-

KHS0

KS
2

+H 0.
2

Toward oxides
crucibles,
(cf.

of metals

KS
2

acts like

K S0
2

4 -f

S0 3 Fused
.

acid potassium sulphate

is,

therefore, used to clean

platinum

by converting

insoluble metal oxides into sulphates

260).

THIOSULPHATES.
Test for Sulphates.
phate,
nitric
i. e.j

249
a soluble
sul-

We

test for

chloric acid

for SO 4 ions, by adding dilute hydroand barium chloride solution, or dilute acid and barium nitrate solution. If a white
is

precipitate

formed, the solution taken probably

contained a sulphate.

Ba+2 Cl+2 Na+S0


The

79).

BaS0 4 1 +2 Na+2 Cl.


barium sulphate, are Calcium sulphate

insoluble sulphates, besides


soluble

those of lead and of strontium.


is difficultly
(cf.

268. Thiosulphates. 2 S2 O 3 Thiosulphuric acid, of one-fourth its acid with oxygen resulphuric "= its salts thion sulphur) placed by sulphur (" are called thiosulphates.
,

is

The most important thiosulphate is the sodium This is made by boiling a solution of salt, Na^Os.
sodium sulphite with sulphur.
.

Na SO +S
2 3

This reaction corresponds to the oxidation of sulphites to


sulphates
(cf.

259).

When sodium
acids,
it

thiosulphate

is

treated with dilute

breaks
2

down

as represented

Na
It

S 2 O 3 +2

HC1

by the equation,
2 3

NaCl+H S0 +S.

decomposes, therefore,

like

a sulphite plus sulphur.

250

SULPHUR AND

ITS COMPOUNDS.

Sodium thiosulphate
of converting chlorine

is

a reducing agent capable

iodine into hydrochloric and hydriodic acids, respectively. It is therefore used to destroy the excess of chlorine in the process
of bleaching.
It

and

has the power to dissolve

silver

chloride, bromide, iodide, etc., is, therefore, used " " in in fixing negatives photography. Its technical

and

name
"

is

"

hypo/'

from

its

old

chemical

name,

hyposulphite of soda."
269. Exercises.
1
.

75

g. of

2.

How many grams of sulphur dioxide can be made by roasting iron pyrites? How many liters at 20 C. and 740 mm.? How many grams ferrous sulphide are needed to give,
1.

with dilute sulphuric acid, 25

of

hydrogen sulphide at 10 C.

and 600mm.?
3.

How much sulphuric acid was there in a solution from which

of barium chloride precipitated 2.836 g. of barium sulphate? If the sulphuric acid was produced by the oxidation of the sulphur in 4 g. of a sulphur ore, calculate the per cent of sulphur in the ore.
4.

an excess

How

sulphite,

could you distinguish between sodium sulphide, and sulphate? Between sodium, ammonium, and barium
use sodium sulphide in a Kipp's apparatus

sulphates?
5.

Would you

to give hydrogen sulphide?

Cupric sulphide?

Lead sulphide?

Why?
6.

sulphide in

Write the molecular equation for the burning of hydrogen air. Give the relative volumes of all the gases used

and produced.
7.

What
salt,

acid

is

product in water

(cf.

formed by heating alum, and collecting the 222)? Alum and salt? Alum and niter?

Alum,

and

niter?

EXERCISES.
8.

251
sulphur dioxide? For

What

drying agents

hydrogen sulphide?

may be used for What ones may not?

9. Silver sulphate is soluble. Write the equation for its action with barium chloride solution. Would you use barium chloride

or nitrate, to test for its sulphate ions?


10.
(cf.

Why?

11.

would you show that "heavy spar" is a sulphate 252 and 254)? Write the equation for the action of hot, concentrated
mercury.

How

sulphuric acid with


543).

With

silver.

With sugar

(cf.

CHAPTER
CARBON AND
270. Carbon.
free

XXII.

ITS

COMPOUNDS.
is

The element carbon


it is

found in a

and an almost pure


anthracite coal;
in petroleum.

and

state as diamond, graphite, found combined in all organic

substances, in carbon dioxide, in carbonates, in coal,

and

Like sulphur, carbon exists in several allotropic forms (cf. 249) the forms usually distinguished being
,

(1)

diamond,

(2)

graphite,

and

(3)

amorphous,

i.

e.,

non-crystalline, carbon.

These three modifications of carbon

differ to

such an extent

that they were long considered different chemical individuals. Their identity is proved by burning them in oxygen; for equal
parts

by weight

of each give equal

amounts

of carbon dioxide.

C+
12

C0
44

2.

32

271.

The Diamond.

The diamond

is

prized for

and its hardness. It is the hardest substance known. The specific gravity of the diamond is 3.5. Acids and alkalies have practically no effect upon it;
its luster, its

strong refractive power,

but when
it

it is

heated to about 700


252

burns, forming carbon dioxide.

When

C. in oxygen, a diamond

AMORPHOUS CARBON.
is

253

it is

heated between the poles of a powerful battery changed into graphite.


artificially

Diamonds have been made

by

crystallizing carbon

from solution in melted iron. This process usually gives graphite, but if the melted iron cools under great pressure the carbon appears in the form of small diamonds. The necessary pressure is secured by chilling the exterior of the mass of iron; the contraction of the exterior thus causes great pressure interior of the mass.

upon the

So far as known, no artificial diamonds yet made are large enough to have any commercial importance.

Graphite is sometimes found but usually in an amorphous form. Its crystallized, is about 2.25. It owes its name, specific gravity " black lead," to a confusion of names. Graphite is a good conductor of heat and of electricity. Owing to its friability it is used to make " " Mixed with clay it is the material lead pencils. of graphite crucibles, which are used in making " " Other uses are: To protect iron steel. crucible
272. Graphite.

from the air, as in stove shot, and as a lubricant.


Graphite
is

polish, to coat grains of

produced

artificially (cf.

271)

by

crystallizing

charcoal from molten iron and steel.

273.

-- The amorphous forms Amorphous Carbon.

of carbon include the several varieties of coal, gas carbon, coke, charcoal, and lampblack; all of these

254
are

CARBON AND ITS COMPOUNDS.


formed by the
charring,
i.

e.,

carbonization, of

animal or vegetable substances.


Carboniza274. Natural Carbonization ; Coal. tion has taken place in nature on a large scale. Vegetable matter, accumulated in certain localities

through many generations, and decaying in the absence of air, was without doubt the material from

which coal was formed. This partially decayed matter was probably much like peat. When the peat was buried under sediments, and thus subjected to water and pressure, a slow carbonization
as a result gaseous products, such as natural gas, etc., passed off, and the excess of carbon remained behind.

took place;

The
Thus,

varieties of coal

owe

their origin to the different degrees

of water-action
soft,
i. e.,

and pressure to which the peat was subjected.


bituminous, coal contains many gaseous subits burning with a large flame and much
is

stances, as

is

shown by

smoke; anthracite coal, on the contrary, and burns with a small flame.

nearly pure carbon,

The table on the following page shows the approximate composition of wood and of several varieties of coal. The difference between the sum of the parts per cent and 100 represents in each case the ash, or mineral matter, of the coal. The artificial 275. Artificial Amorphous Carbon. carbonization of wood produces wood charcoal and
--

ARTIFICIAL AMORPHOUS CARBON.

255

lampblack; that of soft coal, coke and gas carbon; that of animal matter (bones, blood, etc.), animal
charcoal

and

bone-black.

256

CARBON AND ITS COMPOUNDS.

to the escape of volatile substances.

The gaseous products were formerly used as illuminating gas; the liquid parts consist of wood spirit (methyl alcohol), acetic acid, etc.

Fia. 61.

Wood charcoal is used in the reduction of iron from


disinfectant. It absorbs large quancertain gases: ninety volumes of ammonia or nine volumes of oxygen are known to have been
its

ores

and as a

tities of

taken up by one volume of box-wood charcoal. Charcoal owes its action as a disinfectant to its power of absorbing noxious gases, along with oxygen, in
its pores.

The oxygen destroys the

bacteria in the

other gases.

Coke and Gas-Carbon. Coke is the residue left when soft coal is distilled; gas-carbon is the volatile coke condensed upon the walls of the retorts. Gas-carbon is metallic in character and a good conductor of electricity;
of electric cells
it is

used for the negative plates

and for the pencils of electric arc-lamps.

CARBON DIOXIDE.
Coke
is

257

metals from their ores.

used chiefly in metallurgy to reduce the It is also a fuel.


in the distillation of coal con-

The volatile products obtained


sist of

illuminating gas, coal-tar (the source of


etc. (cf.

many

organic

compounds), ammonia,

204).

Animal charAnimal Charcoal and Bone-black. and bone-black are used to destroy organic colorWhen a solution of brown sugar, for ing matter.
coal

example,

is filtered

becomes colorless. same way.

through bone-black, the solution Vinegar may be clarified in the

the volatile products Usually the bones are deprived of their gelatine before being carbonized. In either case the animal charcoal obtained contains the mineral matter of the bones.
distilled destructively

When

bones are

consist largely of bone-oil.

There are Occurrence. 276. Carbon Dioxide two compounds of carbon and oxygen, viz., carbon monoxide and carbon dioxide; of these the latter is
;

by far the more important. Carbon dioxide is present in the air, in some mineral springs, and in certain localities where it Ten thousand parts by escapes from the earth. volume of air contain, on the average, about 3.5
parts of carbon dioxide
(cf.

193).

Carbon Dioxide Exhalations. At Herste, near Driburg, Germany, certain borings made in 1894 struck carbon dioxide
at a depth of 148.5 meters.
place,

violent outburst of the gas took

no

less

than 40,000,000

liters

escaping daily.

The carbon

258
dioxide

CARBON AND ITS COMPOUNDS.


was 99.84% pure.
Thousands
of kilograms were lique-

fied daily.

The origin of the carbon dioxide was probably the action of certain silicates, i. e., salts of silicic acid, 2 Si0 3 upon calcium

carbonate.

277. Preparation of Carbon Dioxide. laboratory, 'carbon dioxide is commonly

In

the

made by

decomposing a carbonate by an
generally used
is

acid.
3.

marble,

CaCO

marble with hydrochloric acid equation,


3

is

The carbonate The reaction of represented by the


C0 T+H 0).
2 2

CaC0 +2HCl

CaCl 2 +H 2 C0 3

(i.

e.,

Evaporation of the solution, after


,

all

action ceases, gives


etc.

calcium chloride, CaCl 2 the substance used to dry gases,

colorless gas.
all

Carbon dioxide is a 278. Physical Properties. It has the slightly acid taste known to "

who

drink

soda water."

It is

about one and

one-half times as
g.

heavy as air; one liter weighs 1.97 under standard conditions. Gaseous carbon dioxide may be condensed to the

liquid state at ordinary temperatures of about fifty atmospheres; above 31

by a pressure

C., however, gas cannot be If liquid carbon dioxide is liquefied by pressure. allowed to evaporate rapidly, it solidifies, forming a

its

critical

temperature,

the

white mass like snow. When liquid air (cf. 198) evaporates, solid carbon dioxide is usually left
behind.

CHEMICAL PROPERTIES.
About ten
annually.

259

million kilograms of liquid carbon dioxide are used

Water absorbs about


of carbon dioxide

times its own volume under standard conditions; with


1.8

increase of pressure the amount increases (cf. 83). the excess of pressure is removed from water surcharged with carbon dioxide, much carbon dioxide " soda water," and escapes; hence the sparkling of

When

also

of spring water, dioxide in solution.

which usually has carbon

Carbon dioxide does 279. Chemical Properties. not allow ordinary burning to continue in it any more than water does, and for the same reason.
oxide

Because of its inability to support combustion, carbon diis used to extinguish fires. For this purpose it is gener-

ated in a strong reservoir by the action of dilute sulphuric acid upon sodium carbonate.

Na C03+H S0
2
2

Na 2S04+H 2C0 3
is

(i. e.,

H 0+C0
2

2 ).

The

resulting gas

directed in a stream

upon the

flames.

Very

strongly burning substances, however, con-

tinue to burn in the gas;

examples are sodium and

magnesium.
The equations for the
dioxide are,
(1)

action of burning sodium upon carbon

Na+C0

2
2

NassO+C.
.

(2)

Na20+C0

Na2 C03

260

CARBON AND ITS COMPOUNDS.


carbon dioxide is passed over red-hot carreduced to carbon monoxide (cf.

When
bon
286).

(Fig. 62) it is

CO +C
2

2 CO.

The volume of the carbon dioxide formed by the union of a given volume of oxygen with carbon is
CARBON

>CO 2

FIG. 62.

equal thus:

to the

volume of

the oxygen.

Or we may

state

it

gram-molecular volume of oxygen gives a 145). gram-molecular volume of carbon dioxide (cf.

C+0

C0

2.

Of the volume of the carbon nothing can be stated because carbon cannot readily be obtained in the gaseous state.

280. Other Sources


(a)

and Uses of Carbon Dioxide. When an aqueous solution Fermentation.

of cane sugar or grape sugar is subjected to the action of the yeast plant, the sugar is decomposed; the chief products are ethyl alcohol, C 2 5 OH, and carbon

BAKING POWDERS.
dioxide.

261

The alcohol remains in solution, but of the carbon dioxide escapes in gaseous form.
Fig. 63

most

shows some character-

istic

yeast plants in the process

of budding.

The

decomposition
is

of

sugar by yeast sugar


is

called al-

coholic fermentation.

a
of

Grape complex comFIG. 63.

pound C 6 Hi2 O 6

the

formula
is chiefly

its decomposition in fermentation according to the equation,


;

CO +2 C H OH.
2 2 5

The brewer
(6)
is

uses fermentation to produce alcoholic

liquors; the baker, to raise bread.

Baking Powders.
called

Ordinary baking powder


tartrate,

a mixture of potassium hydrogen


"

KHC H
4

(commonly
bicarbonate,
e.

cream
3,

of tartar "),

and sodium

NaHCO

g.,

corn-starch.

The

with some diluting substance, ingredients act upon each

The equation other only when moist or in solution. for the decomposition of baking powder is,

KHC H
4

+NaHC0

KNaC H O
4 4 4 4
6

+H CO
2
'

3.

The substance
Salt."

KNaC H O

is

called

Rochelle

262

CARBON AND ITS COMPOUNDS.

Theoretically, any substance that will liberate carbon dioxide from sodium bicarbonate might be used in place of cream of tartar, but practically a substance must be used that will not form a residue injurious to the human system.

"

Acid Phosphate
.

"

baking powders contain so-

dium bicarbonate and calcium hydrogen phosphate, CaH 4 (PO 4 ) 2 The calcium hydrogen phosphate liberates carbon dioxide

from sodium bicarbonate, just

as cream of tartar does.


to Life. Subcarbon their usually give by containing oxidation carbon dioxide. The same result follows whether the oxidation is slow or rapid. Hence all

281. Relation of

Carbon Dioxide

stances

decay, as of of this gas.

wood, paper,

etc., results in

the formation

Carbon dioxide fails to support animal


dioxide
is

life,

not because carbon

poisonous, but because animals cannot extract from it the oxygen necessary for respiration. Besides, the presence of

even a
the
air,

little

more than the normal amount

of carbon dioxide in

say, 7 or 8 parts in 10,000, prevents the proper exit of

carbon dioxide from the lungs.

enormous quantity of carbon dioxide constantly poured into the air by the respiration of animals and plants does not accumulate until it destroys higher animal life is due largely to the
fact that the

The

agency of vegetation. To plants, carbon dioxide


for chlorophyll-producing,
i.

is

an important food;

e.,

green, plants are able

CARBONATES.
to convert carbon dioxide

263

and water, in the presence of light, into sugar, starch, wood, and the various compounds of carbon, hydrogen, and oxygen of which most vegetable products consist.
The
follows
:

natural cycle through which carbon dioxide passes

is

as

(1) Plants, by means of energy derived from the sun, change carbon dioxide and water into plant tissue; (2) Animals, appropriating the stored-up energy of plants, give it forth in their activities and return carbon dioxide to the
air.

The aqueous solution of 282. Carbonic Acid. carbon dioxide has slightly acid properties and gives carbonates with soluble bases; hence the substance

H C0
2

carbonic acid

probably exists in solution.

is thus carbonic anhydride. Carbonic acid cannot be isolated; for it breaks up very readily into carbon dioxide and water.

Carbon dioxide

H CO
2

H 0+CO
2

In

its instability

carbonic acid
(cf.

is

like

ammonium

hydroxide

and sulphurous acid

203 and 259).

When carbon dioxide is passed 283. Carbonates. metallic into solutions of hydroxides it is absorbed,
forming carbonates.
Thus, sodium hydroxide and carbonic acid (carbon dioxide with water is probably carbonic acid) react according to the
equation,
2

NaOH+H CO
2

3 (i. e.,

C0

+H O)
2

>

Na2CO3 +2

H O.
2

264

CARBON AND ITS COMPOUNDS.

A similar reaction takes place when carbon dioxide passed into a solution of calcium hydroxide (limewater); but in this case the carbonate formed is As a result the lime-water becomes insoluble.
is

"

milky."

The equation

is,

Ca(OH) 2 +H2 CO 3
With
analogous.

CaC0

+2 H 0.
2

baryta-water (barium hydroxide solution) the result

is

Ba(OH) 2 +H 2 C0 3

BaC0

3 1

+2 H 0.
2

// a gas forms a white precipitate on being passed into lime-water or baryta-water, we generally assume
that the gas is carbon dioxide (cf. 193). All the common carbonates except those of sodium, potassium, and ammonium are insoluble in pure
water, and are, therefore, precipitated when one of the three soluble carbonates is added to the solution
of a metal salt.
Thus, sodium carbonate gives with calcium chloride a precipitate of calcium carbonate.

CaCl 2 +Na 2 C0 3

CaC0

2 NaCl.

Most carbonates except potassium decompose, when

those

of

sodium and

heated, into the corre-

sponding oxides and carbon dioxide. Thus, marble gives, when heated, quicklime and carbon dioxide. These recombine when cold.

CaCO ^= CaO-f CO
3

2.

BICARBONATES.

265
like

other

Ammonium carbonate is, of course, decomposed by heat, ammonium salts. It is often' called " sal volatile."

of identifying a carbonate is with a dilute acid and then to prove that the escaping gas is carbon dioxide.

The common method


it

to treat

If carbon dioxide is passed 284. Bicarbonates. into lime-water long enough, the precipitate of calcium carbonate, which is formed at first, will be

redissolved.

hydroxide. stood by comparing


acid

similar result takes place with barium This phenomenon may be best under-

it with the action of carbonic and water) upon sodium carbon dioxide (i. e., a reaction represented by carbonate (cf. 267)

the equation,

Na C0
2

+H C0
2

3 (i.

e.,

CO

+H O)
2

NaHC0

3.

is sodium hydrogen carbonate (called, when it is heated gently it breaks sodium bicarbonate); also, up into sodium carbonate, carbon dioxide, and water.

The substance ftaHCOa

NaHC0

Na C0 3 -f H 2C0 3
2

(i. e.,

H 0+C0

2 ).

In a similar way an excess of carbonic acid converts calcium carbonate into calcium hydrogen carbonate, Ca(HC0 3 ) 2 The precipitate of calcium carbonate
.

redissolves,

therefore,

owing to the formation of


is

calcium bicarbonate, which is,

soluble.

The equation
3) 2 .

CaC0

+H C0
2

Ca(HC0

266

CARBON AND ITS COMPOUNDS.


is,

Calcium bicarbonate
decomposes, when
its

solution

however, very unstable; it is heated, into calcium

FIG. 64.

carbonate,

carbon dioxide, and water.

Hence
on

the

precipitate of calcium carbonate reappears

boiling.

NATURAL CARBONATES.
The behavior
of calcium carbonate with

267

an excess of carbon

dioxide explains the solubility of limestone in natural waters which contain this gas; and the ease with which calcium bicarbonis decomposed explains why most waters deposit their limestone upon the walls of vessels in which they are heated (cf. 70).

ate

In many limestone regions underground waters are charged under pressure with carbon dioxide, and therefore take up large quantities of limestone; subsequently the carbon dioxide escapes, and the
limestone
often
is

take

These limestone deposits deposited. on beautiful and fantastic forms, as


See Fig. 64.

stalactites, etc.

285. Natural Carbonates. natural carbonate is limestone,


tities of this

The most abundant

CaCO

3.

Large quan-

substance are distributed over the land

and in the

sea.

Marble is a finely crystallized limestone. Iceland spar is almost pure calcium carbonate; it occurs in large crystals. Coral is limestone taken from the sea by the coral polyp and The shells of most water left as a residue when the polyp dies.
animals are largely limestone.

natural mixture of calcium and

magnesium

car-

bonates called dolomite is also very abundant; it is the chief component of whole ranges of the Alps mountains.

magnesium carbonate. and Sodium carbonate potassium carbonate exist


Magnesite
is

natural

in the soil of

many

places.

The ashes
those
of

of sea-plants

contain sodium

carbonate; carbonate. potassium

land-plants,

268
Both

CARBON AND ITS COMPOUNDS.


of these carbonates are used in large quantities

and are sodium carbonate, on an enormous scale (cf. 414). A large and valuable deposit of almost pure sodium carbonate occurs at Owen's Lake, California.

made

synthetically, especially

286. Formation of Carbon Monoxide.

Carbon

monoxide

produced by the reduction of carbon dioxide by red hot carbon (cf.


is

Fig. 62). versible.


2

The

reaction

is

re-

C0 +C
reaction
is

2 CO.
same

A common illustration of the

seen in every coal fire. The coal at the bottom (Fig. 65) burns to carbon dioxide; but as
it
is

through the bed of reduced to carbon monoxide. The carbon monoxide then burns at the top of the bed of coal to carbon dioxide.
FIG. 65.

this gas passes

heated coal

CO+O

2C0

2.

287. Laboratory

Method.

The common method

of preparing carbon monoxide is to heat crystallized 2 oxalic acid, 2 O, with concentrated sul2 C 2 O4.

phuric acid.

The sulphuric acid removes both the water of crystallization and the water formed by the decomposition of the oxalic acid.

H CA
2

H 0+COT+C0
2

T.

PROPERTIES.
The carbon
dioxide
is

269

sodium hydroxide
does not combine.

solution, with

removed by passing the gases through which the carbon monoxide


sulphuric acid give,
first,

Sodium formate and concentrated

formic acid, and then carbon monoxide.

NaHS0 +(H CO NaHC0 +H S0 H C0 T 0+C0 (H


2 2 4
4

2 ).

2)

Another method

of

making carbon monoxide

is

to

heat

4 Fe(CN) 6 (called, also, potassium ferrocyanide, siate* of potash "), with concentrated sulphuric acid.

"
yellow prus-

288. Properties.

Carbon

monoxide

bears

to

a relation similar to that which formic acid, dioxide carbon bears to carbonic acid. This is evident
2 2,

H CO

from the formulas.


Formic
acid,

Carbonic acid,

H C0 H C0
2 2.
2

3.

Carbon monoxide, CO. Carbon dioxide, C02.

Water and carbon monoxide do not

unite, however, under ordinary conditions. When carbon monoxide is passed over sodium hydroxide at 160 C., the two combine to give sodium formate:

NaOH+CO
Carbon monoxide
is is

NaHCO

2.

a colorless gas; when pure


"

it

almost odorless.
is

It is popularly

gas" and

familiar to every one

known as coal who has used

It burns with a beautiful, blue The flame is best carbon dioxide. flame, giving observed when fresh coal is put upon a hot fire.

anthracite coal.

270

CARBON AND ITS COMPOUNDS.


it is

is

Because of the ease with which a powerful reducing agent (cf.

oxidized, carbon

monoxide

482).

CuO+CO

Cu+C0

2.

Unlike carbon dioxide, carbon monoxide is extremely poisonous; air 'containing one per cent of it

produce fatal results. One liter of carbon monoxide weighs 1.25 g. under standard conditions. The gas has been liquefied at 141 C., its critical temperature, by a pressure of 35 atmospheres.
will

Carbon 289. Cyanogen. to form a gas called cyanogen,


or silver cyanide,

and nitrogen combine C 2 N 2 Cyanogen may


.

be prepared by heating mercuric cyanide,

Hg(CN) 2

AgCN.
is,
2

With

silver

cyanide the equation

AgCN

Ag+C N
2

KCN,

way is to allow a solution of potassium cyanide, drop by drop into a hot solution of cupric sulphate. Cupric cyanide, Cu(CN) 2 is first formed, but at once breaks up
cheaper
to
fall
,

into cuprous cyanide,


(1) (2)

Cu (CN) 2 and
2
,

cyanogen.
.

CuSO.j+2
2

KCN

Cu(CN) 2

Cu(CN) 2 +K 2 S0 4 Cu 2 (CN) 2 +C 2 N 2
.

Cyanogen is a colorless, sweet-smelling gas. It burns with a beautiful, lavender-colored flame, forming carbon dioxide and nitrogen.

C N +2 O
2

CO

+N

2.

METHANE.

271

Cyanogen is so poisonous that no one but an experienced person should make it in quantity, and then only where there is a strong draught.
Hydrocyanic, or prus290. Hydrocyanic Acid. is acid sic, extremely poisonous. It may be made by treating cyanides, e. g., potassium cyanide or potas-

sium ferrocyanide, with dilute sulphuric

acid.
.

KCN+H S0
2

>

KHS0 +HCN T
4

It is a colorless, sweet-smelling liquid, boiling at

27

C.

Compounds of Carbon and Hydrogen. The number of compounds formed by carbon and hydrogen is very large. At present we shall consider
291.

only four,
lene,

viz.:

methane,

CH

ethane,
2.

ethy-

4,

and acetylene,

CH
2

All are colorless

gases.

292.

Methane.

in the destructive distillation of coal,

Methane, or marsh gas, is formed and is, therefore,

present in illuminating gas


(cf.

297).

It is

the old process formed in nature by the decay of


leaves, twigs, etc.,

made by

organic matter,

e. g.,

under water;

marsh gas." The presence of the hence the name gas may be observed by disturbing the material at
the bottom of most stagnant pools, especially in

"

summer.

272

CARBON AND ITS COMPOUNDS.

Marsh gas also enters coal mines; here its mixture with air " forms the dreaded "fire damp (damp = gas; cf. Ger. Dampf.), which explodes with frightful violence when ignited. It was
to avoid these explosions in mines that " " brated 30). safety lamp (cf.

Davy made

his cele-

Methane forms over ninety per cent of tne gases% that escape from petroleum wells. Marsh gas is commonly made in the laboratory
by heating a mixture of sodium acetate, NaC 2 H 3 2 The gas thus sodium hydroxide, and quicklime.
,

produced

is

not pure, however;

it

contains hydrogen

and other

impurities.

An approximate equation is,

NaCzHaOz+NaOH
gas

Na CO
2

+CH

4 T

The equation representing the combustion of marsh


is,

CH +2 O
4

C0 +2 H
2

O.

293. Ethane.

Ethane

is

formed

along

with

marsh gas
Its

in the decomposition of many organic substances, and is a constituent of illuminating gas.

6.

composition is represented by the formula, It burns with an almost colorless flame.

as

In burning, ethane produces carbon dioxide and water, just marsh gas does, but the relative proportions are different.
is

This fact

shown by the equation,


2

C H6
2

>

CO +
2

H 0.
2

294. Ethylene.

Ethylene

may

heating ethyl alcohol,

H OH,
5

be prepared by with concentrated

ACETYLENE.
sulphuric
acid
to

273
C.

above 140

The

following
:

equation represents in part what takes place

H OH
5

H +H O.
4
2

Ethylene is present in illuminating gas; it burns with a bright, luminous flame, producing carbon
dioxide

and water.

C
absorb

H +3 O
4
i

CO +2 H O.
2
2

The most remarkable property


chlorine

of ethylene is its power to and bromine, giving ethylene chloride and

bromide.

Thus,

C 2H4

+ 2 Br

C2H4Br

2.

Both the

chloride

and the bromide are heavy,

colorless oils.

Like the other compounds of and carbon that have been mentioned, hydrogen in is illuminating gas. It is formed present acetylene when a Bunsen burner burns at the base instead of at the top, and may then be recognized by its penetrat295. Acetylene.

ing odor.

Acetylene has been formed by passing an electric spark between carbon terminals in a vessel of hydrogen.

2 C-{-H2
Acetylene
of certain
is

>

now made on a commercial


The
carbide

scale

of water containing a little hydrochloric acid


rnotals.

by the action upon the carbides


is

commonly used

calcium

274
carbide,
is

CARBON AND ITS COMPOUNDS.


CaC
2.

The decomposition represented by the equation,

of this substance

by water

CaC +2
2

C 2H 2 +Ca(OH) 2
air,

Acetylefle

In the

acetylene burns with a

Flame

Air

very smoky flame. With a proper burner the flame is of dazzling whiteness and without soot.
2

C 2H 2 +5

C0 +2 H 0.
2 2

Acetylene is readily condensed to the liquid state. Ordinary mixtures of gaseous acetylene and air
are very explosive.

When
silver

acetylene

is

passed into solutions of cuprous and of


of

containing an excess " are " acetylides precipitated.


salts

ammonium

hydroxide,

Cu 2 Cl 2 +C 2 H
chloric acid, they give

Cu 2 C

+2

HC1.
excess of hydro-

These are explosive when dry. If treated with back acetylene.

296. Illuminating Gas. Illuminating gas is a mixture of several gases already studied. These gases may be divided into (a) combustible gases and
(6)

impurities.

The
dioxide.

impurities are

chiefly

nitrogen

and carbon
:

The combustible

gases are of two kinds

(2)

(1) Those that burn without giving light, and those that burn with luminous flames.

ILLUMINATING

GAS.

275

The non-illuminating gases are hydrogen, methane, and carbon monoxide; they make up about ninety The illuminating per cent by volume of the gas.
gases
ethane,

are

the

so-called

"

heavy hydrocarbons/'
,

and, etc., propane, C 3 8 butane, C 4 Hi usually, small amounts of ethylene and acetylene. Two general processes are employed in making
,

illuminating gas
(1)
(2)

"

The The

distillation of soft coal.

"

water-gas

process.

297. Illuminating

The

old process of

Gas by Distillation of Coal. making gas is carried out as shown

in Fig. 67.
Soft coal in the retorts (there are usually several retorts, one is heated by the furnace to the temperature of

over the other)


decomposition.

The

volatile products pass off

through a pipe

FIG. 67.

276
into the

CARBON AND ITS COMPOUNDS.


"

hydraulic main." which condenses much tar,

The hydraulic main


etc.,

from the

gas.

From

contains water, the main

" the gas passes through the condenser/' which stands over and is more of the tarry products are cooled, water; here the gas condensed.

From
gas
is

"scrubber"; into

the condenser the gas passes through the coke tower, or this water is sprayed, and the illuminating

thereby freed from soluble gases, such as ammonia and

hydrogen sulphide. From the " scrubber " the gas passes into the " purifier." The purifier is a large box containing trays of slaked lime;
this substance

removes carbon dioxide and traces of hydrogen


it is dis-

sulphide. The gas then enters the gas holder; thence tributed to the community through the service pipe.

Many other valuable products besides illuminating


gas are obtained by the distillation of coal. ammoniacal liquors of the condensers and

The
coke

towers are the sources of ammonium compounds the tar of the hydraulic main and con204) (cf. densers gives, when distilled, the important sub;

stances

benzene,

toluene,

naphthalene, etc.;

phenol (carbolic the residue in the retorts


275).

acid),
is

coke

and gas carbon

(cf.

The composition
by
the old process
is

shown

of a representative illuminating gas made 299. in the table accompanying

Within recent years 298. Water-gas Process. the for the old process production of artificial gas has been almost entirely displaced by the "water " process. In this process steam is passed over gas

277

278

CARBON AND ITS COMPOUNDS.

white-hot anthracite coal.


place are represented
(1)
(2)

by
2

The reactions which take the equations, -

C+2 H
C0
It
2

C0 +2 H
2

2.

-hC

CO.
is

The mixture
"

of carbon

water-gas. may be used directly for fuel, but not for lighting, since it burns with a colorless flame. For the conversion of water-gas into an illuminat" " enriched ing gas, the water-gas is by the addition of petroleum hydrocarbons. The process of making an illuminating water-gas will be understood from
Fig. 68.
heated to white heat in the " generator " " by means of a blast of air forced through the coal by a blower." The blast of air is then cut off, and superheated steam is forced over the coal, reacting with it, as already shown, to form carbon monoxide and hydrogen. The mixture of these two gases is then
Anthracite coal
is

"

monoxide and hydrogen

superheaters," in which light petroleum oils decomposed by heat. Here the water-gas obtains marsh gas and the hydrocarbons which give ordinary gas its
forced into the
are being

"

illuminating power. From the superheaters the gas passes through the " scrub" and the " condenser," in which the undecomposed petrober leum and any carbon dioxide, etc., are removed.

299. Comparison of the Two Kinds of Gas.~ The composition of two samples of illuminating gas, one made by the distillation of coal and the other " " by the water-gas process, is given in the following
table:

PINTSCH AND PRODUCER GASES.

279

280

CARBON AND ITS COMPOUNDS.


is

Producer gas
hot coke or coal.

a fuel gas

made by passing air through white


about

It usually has

30%

of carbon monoxide,

the remainder being the nitrogen of the air, and carbon dioxide formed by oxidation of some of the carbon monoxide.

301. Exercises.
1.

cupric oxide,

How
2.

of carbon are needed to reduce 15 grams CuO, if the carbon is oxidized to carbon dioxide? many grams of carbon dioxide are formed? What volume of carbon dioxide at 30 C. and 730 mm. can

How many grams

be produced from 840 grams magnesium carbonate, MgC0 3 ? 3. How many grams of sodium bicarbonate are needed to give, when heated, 36 liters of carbon dioxide? (Cf. 284.) 4. If 50 1. of water-gas ( 299) were burned, how many grams
of water
tions,

and carbon dioxide would result? Use standard condiand consider " hydrocarbons " to be ethane.

5. How many liters of carbon dioxide are formed, under standard conditions, by the combustion of 250 grams carbon

monoxide?
6. Calculate the percentage composition of calcium carbonate, carbon dioxide, oxalic acid. 7. How would you distinguish between sodium carbonate,

sulphite, sulphide,
8.

and formate, chemically? would you distinguish between the gases carbon dioxide, carbon monoxide, oxygen, hydrogen, and ammonia? 9. Calculate the volume, in liters under standard conditions, of 10 g. of each of the following: methane, ethane, ethylene, and

How

acetylene.

of

Calculate also the volume of oxygen needed, and the volumes steam and carbon dioxide produced, in the combustion of
g. of

10

each of these gases.

Use standard conditions.

CHAPTER

XXIII.

FLAMES, LIGHT, AND HEAT.

As stated in Chapter 302. Luminosity of Flames. a is a 28, flame burning gaseous body. The II,

amount
density.

of light given off

the nature of

by a flame depends upon the burning substance and upon its

As an illustration of the influence of density, we may take the case of hydrogen. This substance ordinarily burns in air and in oxygen with an almost invisible flame; if, however, the
hydrogen and the oxygen are very much compressed before ignition, the flame produced by their union is a very brilliant
one.

The illuminating power of all ordinary flames is due to the presence of incandescent solid particles. This may be illustrated by introducing any fine dust into a flame of hydrogen or into the colorless Bunsen flame; the flame at once becomes luminous. In the combustion of substances containing carsuch substances as candles, illuminating bon,
gas,

paper,

petroleum,

wood,

coal,

etc.,

the

luminosity of the flame is due to particles of carbon in the flame.

the glowing of cold object in-

serted into the flame produced by one of these substances becomes covered with soot; and too little
281

282
air,

FLAMES, LIGHT,
or too

AND HEAT.

owing

gas, causes the flame to smoke, to the escape of unburned particles of carbon.

much

A burning candle 303. Structure of Flames. shows practically the same phenomena as the other compounds of carbon just named, and may be taken as representative of them. The burning of a small portion of the wick of the candle furnishes heat enough to melt some of the wax. The wick then draws the melted wax, by capillary action, into the flame, where it is vaporized
and
If

ignited.

the candle flame be examined,

it

will

be found

to consist of several regions, or zones, of combustion, surrounding a central cone-shaped region of

unburned gases. section in Fig. 69.

These parts are shown in

vertical

the region of unburned gases. the luminous zone. It contains solid particles of carbon in a state of combustion.
is

X
B

is

A
-X

is

luminous

the outer mantle of the flame. Being nonit is obscured by the light of B, except
it

at the bottom, where


region.

forms a blue, cup-shaped

portant region (C)


region X.

In addition to the parts just named, an imis believed to exist about the

Being non-luminous, the region C is obscured by the light of B. Whether a flame is to be luminous or nonaffairs in

Fia. G9.

luminous depends upon the condition of the region C


.

NON-LUMINOUS FLAMES.

283
probably as

What
follows
:

takes place in a candle flame

is

The vaporized

paraffin (wax) of the region

(Fig.

69) burns in part in the zone (7, producing enough heat to decompose some of the paraffin vapor into

hydrogen, certain hydrocarbons

(especially

acety-

These substances burn lene), further in the region Bj the carbon burning, as usual, with a bright glow, and thus causing the luminosity of this region. In A the gases and the carbon escapunburned ing through B are more or less completely
solid

and

carbon.

burned.

The decomposi304. Non-Luminous Flames. tion of the combustible material of region (Fig.

--

69) into acetylene, carbon, etc., in the region

re-

quires a definite degree of temperature; hence, if the temperature

C is sufficiently lowered, the flame becomes non-luminous.


of
This
is

what takes place


.

in a

Bunsen

burner

(Fig. 70)
is

When the holes are closed,

the flame

luminous, and has the same

regions as a candle flame. When the holes are opened, the gas rushing past the holes draws in air, the region C is cooled, and

the flame becomes non-luminous.

If car-

dioxide, nitrogen, etc., are introduced, instead of air, the result is the same.

bon

FIG.

70.

284

FLAMES, LIGHT, AND HEAT.


The
--U.O.

regions of a

Bunsen flame

are as follows

(Fig. 71):

X is the region of unburned gas,


dle flame.

as in the can-

C is

is

the light-blue, inner cone surrounding .X". the non-luminous, dark cone. In the
is

candle flame this

luminous.

the purple, outer mantle. In the candle this is the faintly luminous halo surrounding
is

the flame.

305.
of

Heat and Light

of

Flames. -

The temperature

of the different regions

FIG. 71

a Bunsen flame varies greatly. In some parts it is probably 1500 C. If all the heat given off in the burning of carbon and hydrogen were used in

produced is used decomposing hydrocarbons ( 303) into carbon and hydrogen. For a similar reason the temperature of the oxy hydrogen blow-pipe flame (2800 C.) is far below what might be expected. At this temperature water is partly dissociated (cf. 73) hence much of the heat, evolved in the union of hydrogen and oxygen is used up again in decomposin
;

raising the temperature, the flame As it is, a large part of the heat

would be

hotter.

ing steam.

The light-giving power of the Light from Incandescence. incandescent lamp is due to the white-hot carbon, tungsten, or tantalum filament. In ordinary flames the source The hot, but colorless of light is incandescent carbon ( 303).
electric

CANDLE POWER.

285

oxy-hydrogen flame is made to produce light by heating lime 55) to white heat. In the brilliant flames of burning mag(cf. nesium and phosphorus (cf. 24) the light is due to incandescent

magnesium oxide and phosphorus pentoxide, respectively. The Bunsen burner may also be used to give light by heating solids to high temperatures. The Welsbach burner is a Bunsen burner " " " consists of mantle with an incandescent mantle." The the dioxides of thorium and cerium (and sometimes other oxides). The greatest light intensity results from a mixture of 99% Th0 2 and 1% Ce0 2
.

306. Candle Power.

The standard of light intensity is the candle power. This is the illumination produced by a standard candle, burning 7.78 grams (120 grains) per hour. The candle power of some source
of light, of
e. g., an incandescent lamp, Rumford's pho-

may

be measured by means

tometer

(Fig. 72).

The standard
dle
(of

cansize

the

known

as "sixes")

and the lamp are made to throw two shadows of the verFIG. 72
tical

rod side by

upon the screen. When the shadows are of equal density, the illumination from the two lights is equally intense. The intensity of light varies inversely as the square of the distance
side

from the source of light; hence, if the lamp were twice as far from its shadow as the candle is from its shadow, the lamp would have a candle power of 4. If its distance were three times that of the candle, the lamp's candle power would be 9,

and so on.

286

FLAMES, LIGHT, AND HEAT.

and Reducing Flames. The burning hydrocarbon contains both oxidizing and reducing zones; these have an excess
307. Oxidizing
of

flame

of hot oxygen,

and

of hot carbon

and hydrogen,

re-

spectively.

flame at its lower oxidizing region is designated L. 0.; the upper region, U. 0. Within the flame the action is

Thus, the Bunsen flame is an oxidizing outer edge and tip. In Fig. 71 (q. v.) the

The best reducing region is chiefly reduction. the spot that is still slightly luminous when the holes of the burner are partly opened. Substances are oxidized or reduced in " bead " tests (cf. 357
and 399) by being heated persistently in the proper region of the Bunsen flame.
Oxidation and reduction with solids are often carried out in flames produced by the mouth blowpipe (Fig. 73). The luminous flame, 4 to 5 cm. high, is used. The assay (substance
tests

The Mouth Blowpipe.

to be tested)

is placed in a depression hollowed out near one end of a block of charcoal. Air blown into the larger

end

of the blowpipe

comes out at the


tip
is

tip in

a small,

rapid stream.

duced

is

held so that the flame proinclined about 30 to the horizontal.

The

is made by holding the tip of the blowpipe inside the luminous flame, one centimeter above the inner cone of unburned gas. The charcoal

The oxidizing flame

FIG.

73.

is

the assay

held at such a distance, and in such a position, that is in the outer, faintly luminous part of the

blowpipe flame.

The reducing flame is made by placing the tip just at the outer edge of the middle part of the flame. The assay is held

SOURCES OF HEAT.

287

much nearer the blowpipe than in the oxidizing flame best, just at the tip of the inner, light-blue cone of the blowpipe flame.

The common source of 308. Sources of Heat. the high temperatures required for heating and manufacturing operations is the combustion of
fuels.

These consist

chiefly of

carbon and hydrogen,

of hydrocarbons, or of carbon monoxide. In the furnaces used in metallurgy the fuel, the furnace gases, or both, are usually in contact with the ore,

or charge.

called muffle furnaces.

nace
ore
61,

(Fig.

Furnaces which avoid this contact are In the reverberatory fur86 and 485) the furnace gases, alone,
5

reach the charge; while in shaft furnace s

or kilns,
(cf.

and
84,

fuel are usually mixed, or in layers

Figs.

and

88).

Many modern

kilns,

however,

avoid this contact (Fig. 84).


Until recently the oxy-hydrogen blowpipe gave the highest temperature attainable by man. Two other sources of very high temperature are now available: (1) the electric current, and
(2)

thermite.

The

electric current is

used in the electric furnace, invented


of

by Moissan. Electric furnaces are (1) Arc furnaces;


(2)

two general types

Resistance furnaces. arc furnace con-

The
sists of

a crucible and

covering of refractory materials (Fig. 74). The

charge

is

heated by the electric arc.

In the resistance furnace

288

FLAMES, LIGHT, AND HEAT.

the high temperature is developed by the passage of the current through the charge itself, or through other materials having

a high resistance.
to heat.

The energy

of the current

is

thus changed

FIG.

75.

Thermite is a mixture of an oxide, such as iron oxide, with aluminum in a proper state of division. The heat set free when aluminum and oxygen unite is enormous, and may be used to
give a very high temperature at
little cost.

Al+3 Fe 3

4 Al 2

+9

Fe+heat.

309.

Smoke.

The smoke produced in heating and manufacturing has come to be one of the great nuisances of civilization. Smoke consists of the gases produced in combustion (C02, CO, 2 0, S02, etc.)

unburned carbon (soot). The carbon thus lost represents actual waste of fuel, which could be used But the greatest losses in producing heat, if properly burned. due to smoke are the soiling of streets, vegetation, houses, housefurnishings, and clothing, as well as the injury to the health of

and

of solid particles of

persons obliged to breathe smoke-polluted air. Smoke consumers prevent the escape of unburned carbon by bringing supplies of air into intimate contact with it while it is
still

hot.

HEAT OF FORMATION AND DECOMPOSITION. 289


Energy Changes Accompany Chemical Chemical changes result not only in the Changes. formation of new substances, but also in the evolu310.

The tion or the absorption of energy (cf. 27). in of the form electric heat, light, energy may appear
effects, etc.

To illustrate: The union of carbon with oxygen produces carbon dioxide; but at the same time a considerable evolution of heat and light takes place. Since the energy evolved comes
from the carbon and the oxygen, carbon dioxide must possess less energy than the elements which produced it. So, also, water has less energy than the hydrogen and oxygen from which it was formed..

mixture of elements capable of uniting chemimust be looked upon as In the act of union this having potential energy.
cally with evolution of heat

energy is partly given up in the kinetic, i. e., active, form; while in the resulting compound there must be less energy than existed in the elements. Furthermore, to decompose carbon dioxide as much energy must be added as was evolved when the elements
united.

311. Heat of Formation and of Decomposition. The quantity of heat evolved in many cases

of

chemical action has been determined


vi).

(cf.

Appendix,

If

we

call

the

amount

raise the

temperature of one

of heat necessary to gram of water from

290

'

FLAMES, LIGHT, AND HEAT.

C. to 1 C. a calorie we may write the equation for the union of hydrogen and oxygen as follows: -

H +0
2

H 0+ 68,400 calories.
2

This equation shows not only that 2 grams of hydrogen and 16 grams of oxygen unite to form 18 grams of water, but also that by their union 68,400
calories are liberated.
Similarly, for the union of 12
of

grams

of

carbon and 32 grams

oxygen we

may write,

C+0

*
1
is,

C0

+97,000

calories.

For the union of


chlorine the equation

gram
>

of

hydrogen and 35.5 grams of


calories.

H+C1

HCl+22,000

between the energy (calculated as heat) possessed by the elements which united to form a compound and that possessed by the comdifference

The

pound itself compound. The heat

is

called the heat of formation of the

of

decomposition of a compound

is

numerically equal to the heat of formation; that is to say, the quantity of heat necessary to separate a

compound into its elements is just as great as that evolved when the compound was formed from its
elements.

Exothermic and Endothermic Reactions. The heat of formation of water, of carbon dioxide, and of hydrochloric acid is positive (+), heat being
312.

REACTIONS.
evolved
cases,

291
are formed;
is

when

these

compounds

many

however,

exist in

which heat

not evolved,

but absorbed in the formation of a compound from In such cases the heat of formation is its elements.
negative
(

).

heat.

Thus carbon unites with sulphur ( 256) with absorption of The quantity rendered potential is shown in the equation,

C+2 S+ 19,600 calories CS - 19,600 C+2 S


2

CS 2

or

calories.

Similarly,

hydrogen and iodine unite with absorption of heat.

H+I

HI -6,100

calories.

Reactions that proceed with evolution of heat are


called exothermic reactions; while those that take place with absorption of heat are called endothermic reactions.

A
is

substance
it

with

negative
its

heat

of

formation
tion
is

usually unstable.

started,

decomposiproceeds spontaneously, because

When

energy need not be supplied from the outside. One allotropic form is often unstable because in its 249 change to another form heat is evolved (cf.

and

345).

It is a general rule, although it has limitations, that every chemical change that does not require energy from the outside tends to produce those substances which have the greatest heat of formation.

Thus,

if

a mixture of equivalent weights of gaseous fluorine and

chlorine were treated with one equivalent weight of hydrogen, hydrogen fluoride would tend to form, because in its formation

more heat would be

liberated than in the case of hydrogen

292

FLAMES, LIGHT, AND HEAT.

chloride. Again, if fluorine were mixed with hydrogen chloride, the reaction would run from left to right, with liberation of

energy:

HCl+Fo

HF
2

+C1

2.

This rule

is

known
of

as Berthelot's

law of

maximum

work.

313.

Heat

Formation Evolved in Stages.

Just as it makes no difference in the total quantity of heat given out whether a given mass of a combustible burns slowly or rapidly (cf. 25), so the total amount of heat evolved (or ab-

compound

sorbed) in the formation of a compound is the same whether the is formed in one or in several stages.

Thus, the heat of formation of calcium carbonate, CaCOs, is equal to the sum of the heats of formation of calcium oxide, CaO,

and of carbon dioxide, C0 2 plus the heat evolved when calcium oxide and carbon dioxide unite to form calcium carbonate.
,

314. Exercises.
cerium and thorium oxides are Ce0 2 and Th0 2 respecare the formulas of the corresponding nitrates? what tively, The Welsbach mantle consists, originally, of knitted cotton or This is soaked in a solution of the nitrates of cerium and silk. thorium, dried, and set on fire. Write the equation for the
1.

If

resulting decomposition of the nitrates. are the flames of hydrogen and of carbon 2.

Why

monoxide

non-luminous?

Why does kerosene burn with

a smoky, luminous

flame, while that of gasoline is non-luminous? the burning of 3. Account for the differences observed in

and

anthracite coal, charcoal, and coke, on the one hand, and soft coal, on the other.
4.

wood

standard candle and a Welsbach light were 830 cm. and 6m., respectively, distant from the shadows cast on the screen of a Rumford photometer ( 306), when the shadows were

EXERCISES.
of equal density.
light?

293

What was

the candle power of the Welsbach

A 36-candle power electric light and a standard candle shadows of equal density upon the screen of the photometer. What are their relative distances from their respective shadows? 6. Find, in the Table of Heats of Formation (Appendix vi), the values for ethane, ethylene, and acetylene. Which of these three substances is the most stable? The most unstable? Why? Make a similar comparison between water, hydrogen sulphide, and hydrogen iodide.
5.

cast

CHAPTER XXIV.
FLUORINE, BROMINE, IODINE, AND THEIR

COMPOUNDS.
The elements fluorine, chlorine, 315. Halogens. " the halogens/' from bromine, and iodine are called " Greek for and the suffix gen, meaning hals, salt/' " " a constituent of/' as in hydrogen/' etc. Their
binary compounds, are called halides.
e.

--

g.,

chlorides,

bromides,

etc.,

ture;
is

Fluorine and chlorine are gaseous at the ordinary temperabromine is a liquid boiling at about 59 C.; while iodine
off,

a black solid which gives

even at ordinary temperatures,

a beautiful, violet vapor.

-316. Fluorine.
in its
free
is

The element fluorine was known compounds long before it was obtained in the condition. The most common of its compounds
.

calcium fluoride, or fluorspar, CaF2 Fluorspar " derives its name fromfluo, Latin for to flow," and
spar, meaning this substance
in metallurgy.

"

a rock."

The name

is

applied to

owing

to the use of fluorspar as a flux

of

A flux is an easily fusible substance added to the mixture an ore and a reducing agent to promo te fusion of the mixtureThe substance resulting from the union of the flux with the
impurities present
is

usually called
294

"
slag

"
(cf.

482).

HYDROFLUORIC ACID.

295

-dh

i|

IK

296

FLUORINE, BROMINE, IODINE.

a strong acid.
e.

Anhydrous hydrogen fluoride boils at 19 C. The solution is Being dibasic, it forms both acid and normal salts, Both hydrogen fluoride vapor and its g., KHF 2 and K 2 F 2
.

solution are very poisonous.

almost

all

The aqueous solution reacts with the metals, forming fluorides and hydrogen, and with
and
water.

their oxides, forming fluorides

(quartz, sand, etc.) and hydrofluoric acid give silicon fluoride (a gas) and water.
Silicon

dioxide

Si0 2 +2

HF
2

SiF4

+2 H 0.
2

Glass a mixture of silicates (cf. reacts 394) with hydrofluoric acid like a mixture of metal oxides and silicon dioxide. With calcium silicate, CaSiO 3 the equation is, ,

CaSiOa+3

HF
2

CaF +SiF4 1 +3
2

H 0.
2

Hence, when glass is treated with hydrofluoric acid, the silicon present in the glass escapes as SiF4 leaving a depression in
,

the glass.
glass.

This fact
glass
is

is

The

is first

use of in the operation of etching covered with a thin layer of paraffin, and

made

When

in the paraffin by means of a sharp point. the exposed glass is wet with the solution of the acid (a swab of cotton attached to a stick may be used to apply the

a design

drawn

solution) or

is left

in the

vapor of the

acid, the design is etched

into the glass.

Hydrofluoric acid is commonly kept in bottles of paper, covered inside and out with a thick layer of Vessels of lead, platinum, or rubber may paraffin.
also

be used.

PREPARATION OF BROMINE.

297

BROMINE.
319. Preparation of Bromine.

Bromine

is

found

in nature in the combined form, chiefly as bromides.

The most common bromides


(NaBr), of

are those of sodium


of

potassium (KBr), and

magnesium

(MgBr2 ).
Bromides occur in sea-water and in salt deposits. Bromine is prepared by heating a bromide with manganese dioxide and dilute sulphuric acid. The
bromine vapor evolved is condensed in cold receivers. With sodium bromide the complete equation is, -

Mn0 +2 NaBr -1-3 H S0


2 2

MnS0 +2 NaHS0 +Br +


4 4
2

2H 0.
2

This reaction
(

is

like that for the preparation of chlorine


salt,

115) from

common

manganese

dioxide,

and hydrochloric

acid.

There are

three stages:

(1) Sulphuric acid and sodium bromide give hydrogen bromide and sodium hydrogen sulphate.

NaBr+2 HaS04

NaHS04 +(2

HBr).

(2) Sulphuric acid and manganese dioxide give manganous sulphate and oxygen.

Mn0 +H S0
2
2

>

MnS0

+H 0+(0).
2

(3)

Hydrogen bromide and oxygen give free bromine.


(2

HBr) + (0)

>

H 0+Br
2

Bromine may also be prepared by conducting the proper amount of chlorine into the solution of a bromide. With magnesium bromide the equation is, MgBr2 +Cl
2

MgCl 2 +Br 2

298

FLUORINE, BROMINE, IODINE.

Bromine is a brown 320. Properties of Bromine. 3.2 times as as water. Its vapor heavy liquid about has an odor much like that of chlorine, and affects
boils at about 59 C. bromine vapor shows that the density its formula molecule is diatomic; is, therefore, Br2 At about 1000 C. the molecule begins to dissociate into molecules containing only one atom each (cf.

the eyes.

Bromine
of

The

142).

Bromine dissolves in water, carbon disulphide, and other solvents. The aqueous solution is called " bromine water." In the presence of some substance capable of taking up oxygen, bromine reacts with water energetically,

according to the equation,


2

H O-f 2
2

Br,

HBr+O

2.

The oxygen Bromine water


The same
substance
is

is

in the nascent state

(cf.

123).

is

action

thus a good oxidizing agent. goes on more slowly when no oxidizable

present; bromine water thus becomes converted into a dilute solution of hydrobromic acid, HBr.

less active than chlorine, but, like unites with hydrogen and with metals. chlorine, Most bromides are soluble (cf. 130).
is
it

Bromine

321. Hydrobromic Acid. Hydrogen bromide cannot be made in a pure state from a bromide and concentrated sulphuric acid, because some of it is
oxidized

by the

sulphuric

acid.

The product

is,

PROPERTIES OF HYDROBROMIC ACID.

299

therefore, a mixture of hydrogen bromide, bromine, and sulphur dioxide (from the sulphurous acid)
.

(1)
(2)

NaBr+H S0
2

4 4

2HBr+H S0
2

NaHS0 +HBr. H 0+Br -fH S0


4
2 2 2

3.

With
place.

dilute sulphuric acid

only reaction

(1)

takes

To prepare pure hydrogen bromide, a mixture of red phosphorus and water is treated with bromine. Phosphorus tribromide is first formed, and is then
hydrolyzed.
(1)
(2)

P+3

Br 2

PBr 3 +3

HOH

>

PBr3 P(OH) 3
.

[i. e.,

H P0 ]+3 HBr T
3 3

The phosphorous
hydrogen bromide
the gas evolved red phosphorus.
is

acid

is

not

volatile, while

the

is. To remove bromine vapor, passed through a U-tube of moist

322. Properties of

gen bromide,
air,

like

Hydrobromic Acid. Hydrohydrogen chloride, fumes in the

When distilled, dissolves readily in water. the solution behaves like that of hydrogen chloride:
and

a mixture containing 48% of hydrogen bromide passes over at 126 under 760 mm. pressure. The

concentrated aqueous solution has a specific gravity of almost 1.8, and contains 82% by weight of the acid.
Hydrogen bromide begins
73) at about 800
C.;
it is,

to dissociate into
therefore,

its

elements

(cf.

than hydrogen chloride, which begins to dissociate at about 1500 G


less stable

much

300

FLUORINE, BROMINE, IODINE.


IODINE.

323. Occurrence and Preparation of Iodine. The chief source of iodine until recently was the
ashes of certain sea-plants which absorb iodine compounds from sea-water. At the present time the

obtained largely from the Chile saltpeter In these deposits the iodine is found deposits. chiefly as sodium iodate, NaIO 3 Iodine may be set free from an iodide in just the same way that chlorine and bromine are set free

element

is

from
dilute
is,

chlorides
it

and bromides
acid.

respectively,

viz.,

by

heating

with a mixture of manganese dioxide and

sulphuric

representative

equation

Mn0 +2 NaI+3
The
(1) (2) (3)

H,S0 4

stages of the reaction are

NaI+2 H S0 Mn0 +H S0
2
2

(2HI) + (0)

MnS0 +2 NaHS0 +2 H 0+I


4

2.

NaHS04 +(2
2

HI).

MriS0 4 +H 2 0+(0).
T.

H 0+I
2

Iodine

may
2

also

be set free from an iodide by

means

of chlorine or bromine

NaI+Br NaI+Cl 2

(cf.

319).

NaBr+2 I. NaCl+2 I.
Iodine

324. Properties of Iodine.

is,

ordinarily,

an almost black
at about 184
color; it
is

solid, melting at 114

C. and boiling

vapor has a beautiful, violet about 8.7 times as heavy as air.


Its

C.

HYDRIODIC ACID.
Iodine

301

is very soluble in carbon disulphide and in but only slightly soluble in water. It is less ether, active than chlorine or bromine. It stains the skin brown, and imparts an intensely blue color to starch

paste.

Iodine sublimes
to above 600

(cf.

211)

when heated.

C. the molecule of iodine vapor consists Up of two atoms; above this temperature, dissociation takes place. At about 1500 C. only monatomic iodine molecules exist.

325. Hydriodic Acid. Hydrogen iodide is still more unstable than hydrogen bromide. It cannot be made in a pure condition by treating an iodide

with concentrated sulphuric acid for the reason that


the hydrogen iodide reduces the sulphuric acid. The reduction goes not only to sulphurous acid, as in the case of hydrogen bromide, but in part even to hydro-

gen sulphide.
(1) (2)

The equations representing this are, 2 4


2

KI+H S0 2 HI+H S0 (2a) 8 HI+H S0


4

KHS0 +HI; H S0 +H 0+2 I; H S+4 H O+8 I.


4
2

iodide may be made by allowing red and iodine to react in the presence of phosphorus water. Phosphorus tri-iodide is first formed, but is decomposed at once according to the equation, > H 3 P03 +3 HI (cf. PI +3 H 2 321).

Hydrogen

An aqueous solution of hydriodic acid may best be prepared by making use of a property common to chlorine, bromine, and iodine, viz., the ability of each of these substances to decompose hydrogen

302
sulphide.
is

FLUORINE, BROMINE, IODINE.

The sulphur formed,

precipitated;

pletion (cf. iodine is,

being insoluble, hence the reaction goes on to comThe equation in the case of 253).

2I+H S
2

2HI+Si.

sulphide is conducted into a mixture of iodine The sulphur is then the iodine disappears. until water and filtered off, and the filtrate distilled. After the water has passed

The hydrogen

off,

about

a heavy liquid is obtained, which 57% hydrogen iodide.

boils at 126

C.

This

is

326. Properties of Hydriodic Acid. iodide is about 4.4 times as heavy as

Hydrogen
air.

Like
C.

hydrogen chloride and bromide,


in water.

it

is

very soluble

One

cubic centimeter of water at 10

and standard pressure


the gas.

dissolves about 450 c.c. of

Hydrogen and iodine can be made


appropriate conditions.
evolve

to unite

under

When

heat, but absorb it. fact that hydrogen iodide is so unstable

uniting they do not This accounts for the


(cf.

312).

The
steam

dissociation of
(cf.

73).

hydrogen iodide is like that of At any temperature above the

point at which dissociation begins, the decomposition of hydrogen iodide goes on side by side with re-

combination of hydrogen and iodine.


2
If either

HI

H +I
2

2.

product of dissociation is removed from the sphere of action," the dissociation goes on to completion. Thus, if

"

HALOGENS WITH OXYGEN.


silver is placed in hydriodic acid solution, it unites

303
with the
free.

iodine as rapidly as iodine is formed.

Hence hydrogen is set

Ag+2 HI

AgI+H

2.

ready dissociation, hydriodic acid acts as a powerful reducing agent. Oxygen, or any oxidizing agent, gives with it iodine and water.

Because of

its

4HI+0

2H 0+4I.
2

327. Compounds of the Halogens with Oxygen. Only three halogen oxides have been actually made;

although more especially one oxide of bromine are suspected to be capable of existing. The three oxides definitely known are :

Chlorine monoxide, C1 2 O; Chlorine dioxide, C102 or C1 2 O4; Iodine pentoxide, I 2 6


.

Chlorine
boils at

monoxide
C.

is

an unstable liquid which

+5

chlorine

and oxygen.
C1 2

It explodes with violence giving It is the anhydride of hypo-

chlorous acid.

0+H ^=
2

HOC1.

Chlorine dioxide (C1O 2 ) and tetroxide (C1 2 O 4 ) 2 O4. correspond to the nitrogen oxides N0 2 and are formed with violent when conThey explosion centrated sulphuric acid acts upon potassium chlorate. Their preparation should not be attempted

without
cautions.

precise

directions

and extraordinary

pre-

Chlorine dioxide
at about 10

is

a reddish-brown liquid, boiling

C.

304

FLUORINE, BROMINE, IODINE.


is

Iodine pentoxide
at present.
It
is

the only oxide of iodine


stable

known
with

a white,

powder;

water

it

gives iodic acid:


I2
5

+H

it is

iodic anhydride.

HI0

8.

328. Compounds of the Halogens with Oxygen and Hydrogen. Compounds of the halogens with oxygen and hydrogen are called oxygen acids, or They are more numerous oxy-acids, of the halogens.

than compounds with oxygen alone; for they include at least three chlorine acids, three bromine The formulas of these acids, and two iodine acids.
acids are
:

HC10.
Tr nin j HC1 2

HBrO.

known only

>
.

i in its salts

HC10 HC10 4

3.
.

HBr0 HBr04

3.
.

HI0 HI0

8. 4.

When chlorine is 329. Hypochlorous Acid. dissolved in water, a small amount of hypochlorous acid is formed :

(1)

H 0+C1 ^=HOC1+HC1.
2 2

than the forward one.

far more complete apparent when the two acids are set free together from bleaching powder. Chlorine and water are formed.

The

reverse action

(cf.

243)

is

This

is

XC1

IT
:

HOC1+HC1

-H

CaS0 +HOCl+HCl.
4

0+C1

2.

HYPOCHLOROUS ACID.
If,

305

present in the water to added, it unites with the acids as rapidly as they are produced, and the reverse action of (1) does not take place.
is

however, a base
is

which chlorine

(2)

KOC1+KC1+2 H 0.
2

When, therefore, chlorine is passed into a solution of potassium hydroxide, the stages of the reaction are shown by (1) and (2). The products in solution
are potassium hypochlorite

and chloride.

When
a mixed

chlorine

is
:

passed into slaked lime, bleaching powder,

salt, results

/OH HOC1
Ca v

+ \)H HC1
is

/OC1 Ca( X +2H


C1
(cf.

0.

Hypochlorous acid

a weak acid

178).

If chlorine is

passed into water containing suspended calcium carbonate, the hydrochloric acid formed reacts with the carbonate, but the

hypochlorous acid does not.

When

the solution

is distilled,

dilute solution of hypochlorous acid passes over.

HC1+2 HOCl+CaCO3

CaCl 2 +H 2 C0 3 +2 HOC1.
is

The

solution of hypochlorous acid

very unstable.

In the

presence of reducing materials it is a powerful oxidizing agent. This accounts for the bleaching properties of chlorine water and of acidified bleaching powder (cf. 119, 122, and 123). In the

presence of sunlight, chlorine water,


gives off oxygen
(cf.

i.

e.,

hypochlorous acid,

Bleaching powder also gives oxygen when treated with catalyzers, such as cobalt hydroxide, etc.
119).

2 Ca(OCl)Cl

2 CaCl 2

+0

Hypochlorous acid

is

decomposed with evolution of heat.

306

FLUORINE, BROMINE, IODINE.

The oxygen liberated thus owes its great activity (nascent state) to the excess of energy set free at the same time. In concentrated solution hypochlorous acid changes spontaneously to chloric and hydrochloric acids 3
(cf.

331.)

HOC1

HC103 +2 HC1.

330. Chlorous Acid,

H-O-C1 = O.

Chlorous acid does not exist free. Its potassium salt is produced, in solution, when an aqueous solution of chlorine dioxide, C1C>2, is treated with potassium hydroxide.

331. Chloric Acid,

H-O-C1^~.
contains

Chloric acid
this

is

known only
Chloric acid

in its

aqueous solution;
it

may

be

concentrated until
is

40%

of chloric acid.

a powerful oxidizing agent.

formed by conducting chlorine into concentrated solutions of alkalies to complete hot, With potassium hydroxide the comsaturation.
Chlorates are
plete

equation
6

is,

C1 2

KOH+3

KC10 3 +5 KC1+3
from the
chloride

H 0.
2

The

chlorate is separated

by

recrystalliza-

tion from hot water.

The

chlorate, being

much

less soluble

than

the other, separates out first. Just as hypochlorous acid changes to chloric acid and hydrochloric acid (cf. 329), so solutions of hypochlorites change,

when
(1) (2)
(3)

heated, to chlorates and chlorides. Hence the reaction for the preparation of potassium chlorate has the following stages
:

3 Cl 2 +3

(3

HOCl) + (3 HC1).
2 3

6KOH+(3HOC1) + (3HC1) (3KOC1)+3KC1+6H 0. KClO +2 KCL (3 KOC1) By adding the factors and products not eliminated, and sub-

BROMINE WITH OXYGEN,

ETC.

307

tracting the water of (1) from that of (2), we get the complete equation given above. When concentrated acids act upon chlorates, the resulting chloric acid is decomposed with explosive violence (cf. 327).

When
by

hydrochloric acid

is

used, the reaction


it

may

be stopped,

dilution with water, before

becomes explosive.

tions are,
(1)

(2) (3)

KC10 3 +3 HC1 3 HClOa+3 KC1. HC10 3 HC10 4 +2 C10 2 +H 0.


2

2 C10 2

Cl 2 +2

The equa-

2.

332. Perchloric

Acid,

H-O-C1=O.

Perchloric
1.8

^O
acid as
is

colorless, explosive liquid

about

times

heavy
heat.

as water.

Its salts, the perchlorates, are

produced when the chlorates are partly decomposed

by
is

is

In the decomposition of potassium chlorate (cf. 20), a point soon reached at which a considerable increase of temperature needed to continue the evolution of oxygen. The amount of

oxygen evolved up to this point is only one-fifth of the quantity If we stop at this stage, we present in potassium chlorate. obtain a mixture of potassium perchlorate and potassium chloride, as shown in the equation,
5

KC10 3

3
is

KC10 4 +2 KC1+3
much more

0.

The potassium

chloride

soluble than the per-

chlorate; hence these substances lization from water.

may be

separated by recrystal-

Compounds of Bromine with Oxygen and No compounds of bromine and oxygen Hydrogen. been have prepared in a pure condition. With
333.

308

FLUORINE, BROMINE, IODINE.

oxygen and hydrogen bromine forms hypobromous bromic acid, and perbromic acid. Bromine reacts with water as chlorine does (cf. 329)
acid
}
:

H 0+Br
2

HOBr+HBr.

Hypobromites are formed when cold, dilute alkalies are treated with bromine, but with less than is
required for saturation. 2 KOH+2 Br

KOBr

+H 0+KBr.
2

Hypobromites,
agents.

like

hypochlorites,

are

oxidizing

rated with bromine

Bromates are formed when hot alkalies are satuPotassium (cf. chlorates, 331). bromate is a white, crystalline solid, like potassium
chlorate. Heat decomposes it into potassium bromide and oxygen. 2 KBr0 2 KBr+3
3 2.

334.

Compounds
--

of

Iodine

with

Oxygen and

Hydrogen.

Two

oxy-acids of iodine are known;

they are iodic and periodic acids.


lodic acid

(HI0 8

or

H-O-I/9)
it

is

formed by
It

oxidizing iodine with concentrated nitric acid.


is

a crystalline

solid.

iodine pentoxide (I 2 O 5 ) lodates are formed by adding iodine to hot, concentrated solutions of alkalies. With potassium

At 170 C. and water.

breaks up into

hydroxide the equation


6

is,

KOH+6 I

KI0 +5 KI+3
3

H 0.
2

THE HALOGEN FAMILY.


Periodic acid

309

is

HI0 4

or

H O

1=0.
.

/P ^0

Its salts are per-

iodates, e. g.,

sodium periodate, NaI0 4

From the preceding a pages great similarity in the properties of the elements fluorine, chlorine,
335.
it is

The Halogen Family.

evident that there

is

bromine, and iodine. consider that there


is

The
is

close relation

of

these
if

elements to one another

yet more marked

we

a gradation in the properties of these elements in the order of the atomic weights.

Thus, the melting temperatures, the boiling temperatures, and the specific gravities of these elements
rise

fluorine (atomic wt. 19) to iodine (atomic wt. 127). The intensity of the color of these ele-

from

ments
is

also increases with the

atomic wt: fluorine

and

greenish yellow; chlorine, green; bromine, brown; iodine, black.

The gradation observed in their physical properties is true also of their chemical properties. Thus, the elements of lower atomic weight can expel those of higher atomic weight from their
soluble metal salts.

The same gradation


compounds
of

of properties is noticed in the

the

halogens.

Thus,

the

specific

gravity of the hydrogen compounds increases from hydrogen fluoride to the iodide; while the stability of these compounds decreases in the same order.
In the case of the compounds of the halogens with oxygen, and with oxygen and hydrogen, the order of stability is reversed,

310

FLUORINE, BROMINE, IODINE.

iodine forming the most stable ones, chlorine very unstdbk ones, and fluorine none at all.

The same gradation of color seen in the elements themselves appears in many of their compounds. Thus, silver chloride is white; silver bromide, light
yellow; silver iodide, bright yellow. Some of the above (and other) facts appear in the following table
:

PROPERTIES.

EXERCISES.
336. Exercises.
1.

311

How many grams


How

of

bromine can be made from 150 grams


dilute

of potassium bromide sulphuric acid?


2.

by using manganese dioxide and

would you separate a mixture of iodine and sand? Could phosphoric acid be used, instead of sulphuric acid, 3. to prepare hydrogen chloride, bromide, and iodide? Write the
possible equations.

What
must
salts.

Has it any advantages over sulphuric acid? Name three properties an acid are its disadvantages? have to be usable in setting volatile acids free from their

4. How could you distinguish, by chemical means, between a chloride, a bromide, and an iodide? 5. How could you identify a fluoride, e. g., calcium fluoride?
6.

Why

is

potassium fluoride added to anhydrous hydrogen

fluoride in the preparation of fluorine


7.

by

electrolysis?

Write the equations for the action of bromine water upon sulphurous acid; upon hydrogen sulphide; upon iron. 8. What would you use to dry hydrogen bromide and iodide? 9. Give the meaning of the names of the halogens. 10. Write the equation for the preparation of iodic acid. 11. Give the equations for all the stages of the reaction by

which potassium iodate


is

What additional reaction is prepared. necessary to prepare the iodide from the iodate? 12. Write the equations for the action of potassium hydroxide
chlorine dioxide.

upon

Upon

chlorine monoxide.

the anhydride of perchloric acid? 13. 14. A certain compound has the following composition: C, 12.77%; H, 2.12%; Br, 85.11%. At 137 C. and 760 mm. 188 c.c. of its vapor weigh 1 .06 g. Find its formula.
is

What

CHAPTER XXV.
OZONE AND HYDROGEN PEROXIDE.
Oxygen which has been exposed to 337. Ozone. the silent electric discharge possesses new properties. It has a peculiar odor and oxidizing powers not possessed by ordinary oxygen. Thus, it oxidizes silver and mercury at once, whereas these metals are not acted upon by oxygen at ordinary temperatures. These new properties are due to the presence in

the

The name

oxygen of another substance, called ozone. ozone is from the Greek ozein, to smell.
is

The same substance


oxidation.

produced in almost every case of

is the slow oxidation of phosmoist is phosphorus placed in a covered vessel, the phorus. peculiar odor of ozone soon appears. Ozone is formed, also, in

An

illustration of this

If

the electrolysis of water, and appears at the with oxygen.

electrode along

ozone is examined, it is found to contain but nothing oxygen; it is, in fact, an allotropic form When oxygen changes into 249). of oxygen (cf. ozone there is a contraction of volume amounting

When

volume of oxygen taken. Ozone one and one-half times as heavy as is, therefore, oxygen. Its molecular weight is 48 instead of 32;
to one-third of the
312

PROPERTIES OF OZONE.
hence the molecule of ozone contains
atoms, and
The
is

313
three

oxygen

written

O
O
2

3.

relation of ozone to

oxygen
7

is

one of equilibrium:

2 Os.

The forward change

is

accompanied by absorption of heat;


In the reverse change, the energy

hence, the instability of ozone.

reappears, giving nascent oxygen.

338. Properties of Ozone. the oxidizing power of ozone

As might be expected,
is

very great.

Moist

phosphorus and sulphur are converted by it into phosphoric and sulphuric acids, respectively; and

ammonia

is

at once oxidized to nitric acid.

Organic

coloring substances, e. g., indigo and litmus, are at once decolorized by ozone. The bleaching of fabrics on exposure to the air is probably due to the action
of ozone present in the air.
ozone is heated, its molecule is decomposed, and ordiThe reversion of ozone to oxygen is acresults. oxygen nary companied by an expansion of volume just equal to the contraction that takes place when oxygen changes into ozone. Ozone is readily absorbed by oil of turpentine; hence, the amount of ozone formed in a given volume of oxygen may be determined by exposing the ozonized oxygen to this substance. Only about six per cent of a given amount of oxygen can be converted into ozone, because the reverse change of ozone into

When

oxygen soon produces a condition

of equilibrium.

The presence of ozone in ozonized air is readily detected by means of a mixture of potassium iodide

314

OZONE AND HYDROGEN PEROXIDE.


best

and starch paste

upon a

piece of

filter

paper.

The ozone
equation,

sets iodine free,

probably according to the


2

KI+H 0+0
2

KOH+2 I+0

2.

Hydrogen Peroxide. Closely related to and confused with ozone, long it, is hydrogen peroxH O 2 2 ide, Hydrogen peroxide is a colorless liquid about one and one-half times as heavy as water; it possesses remarkable oxidizing and reducing
339.
.

powers.

dilute solution of

hydrogen peroxide
,

may

be

made by adding barium peroxide, Ba0 2 to dilute hydrochloric acid. The equation is, Ba02 +2 HC1 BaCl2 +H2 2 A somewhat better way is to treat a dilute solution of tar.

taric acid

with sodium peroxide,

Na
in air free

+H
is

C 4H40 6

Na 2 2 Na C 4 H 4
.

+H

2.

Sodium peroxide

made by

heating sodium to about 350

C.

from carbon dioxide.

phosphorus is partly immersed in water, it upon the moist air to form both hydrogen peroxide and ozone. Both of these substances are
acts

When

formed, also, by holding a hydrogen flame against a piece of ice.


Hydrogen peroxide is formed in the electrolysis of water, if oxygen is passed into the water at the negative ( ) electrode. The oxygen is reduced by the nascent hydrogen evolved at the
electrode,

PROPERTIES OF HYDROGEN PEROXIDE.

315
in all

rain water

Hydrogen peroxide and snow.

is

found in the

air,

and

340. Properties of

Hydrogen Peroxide.

Hydro-

gen peroxide may be obtained almost pure by distilling a dilute aqueous solution of it at low pressure. The apparatus for distilling at reduced pressure is
essentially as

shown

in Fig. 77.

distilling flask

(A)

is

and a

capillaryj tube (C).

provided with a thermometer (B) The capillary tube allows a very

small stream of air to be


distilling

drawn through the apparatus.


air-tight

The

flask is

connected

with the condenser (D)

and the
is

receiver (E).

indicated

The pressure, in millimeters of mercury, by the manometer (F). The air is exhausted at S
mercury suction-pump.

by a water

or

At 26 mm. pressure hydrogen peroxide boils at 69 C.; under the same pressure water boils at 27 C.; hence the two substances can be separated

316
readily.

OZONE AND HYDROGEN PEROXIDE.

The aqueous solution of hydrogen peroxide has a bitter taste and produces white spots upon the It is a powerful antiseptic. skin.
Hydrogen peroxide decomposes readily, especially in the presence of basic substances. The products are water, and oxygen in the nascent condition;
hence hydorgen peroxide
is a powerful oxidizing It decolorizes indigo, litmus, etc., as ozone agent. does. It at once oxidizes hydrochloric acid to water

and

chlorine.

Hydrogen peroxide acts also as a reducing agent with evolution of oxygen. Thus, it reduces mercuric oxide to mercury and sets oxygen free.

HgO+H
One atom

Hg+0 +H 0.
2 2

of each oxygen molecule (0 2 ) comes from the hydrogen peroxide, and the other from the oxide reduced.

Potassium permanganate solution is at once decolorized by hydrogen peroxide, and potassium chromate and bichromate solutions are changed to a green color. All of these are reductions. Ozone and hydrogen peroxide reduce each other.
3

+H

>

+H 0+0
2

2.

Hydrogen peroxide, like ozone, decomposes with evolution of heat; this accounts for its instability and oxidizing power.

The common test for the presence of hydrogen peroxide in a solution is to add to the solution in a test tube about two or three cubic centimeters of ether, and then one drop of potassium bichromate

COMPOSITION OF HYDROGEN PEROXIDE.


solution.
of

317

When
is is

the test tube

is

shaken, the layer


if

ether

colored a beautiful blue,


present.

hydrogen

peroxide

341. Composition of

drogen

peroxide

is

Hydrogen Peroxide. Hycomposed of 1.01 parts, by

weight, of hydrogen to every 16 parts of oxygen.

weight is 34; hence its formula is 2 The constitutional formula of hydrogen peroxide
Its molecular

2.

is

H-O-O--H.
The
effect of the structure of the molecule,
i.

e.,

the

way

in

which the atoms are united, upon the properties of substances, is admirably illustrated by the differences in the behavior of the two classes of dioxides. Thus, while calcium peroxide (Ca0 2 ), sodium peroxide (Na20o), and barium peroxide (Ba02) give
hydrogen peroxide when treated with dilute acids, lead dioxide (Pb02) and manganese dioxide (Mn0 2 ) do not. The structure
of all true peroxides is like that of hydrogen peroxide. constitutional formula of sodium peroxide, is, therefore,

The

Na
and that
of

Na,
0.

barium peroxide,

The graphic formula

of

Ba
the
dioxides
is

different, that
,

of

manganese dioxide being,

probably,

Mn/'

and that

of lead dioxide

Pb/.

V)
342. Exercises.
of

^o

evolved when a gram-molecular weight hydrogen peroxide gives a g. m. wt. of water (cf. Appendix
i
.

How much

heat

is

vi)?

318
2. If

OZONE AND HYDROGEN PEROXIDE.


oxygen
all.

is bivalent,

write the constitutional formula of

ozone.
3.

Name

bleaching or disinfecting agents.

the substances studied up to the present that are Are any not sources of nascent

oxygen?
4. When 10 g. of a certain solution of hydrogen peroxide are treated with acidified potassium permanganate solution, each drop of the permanganate is decolorized, until 0.15 g. available

oxygen has been added.

What

is

the

% of H

in the solution?

CHAPTER XXVI.
THE NITROGEN FAMILY. PHOSPHORUS, ARSENIC, ANTIMONY, BISMUTH.
A.

Phosphorus.
of

PhosphoPhosphorus is found in nature only in the combined form, chiefly in phosphates. The most abundant phosphate is calcium phosphate, Ca 3 (PO 4 ) 2 Calcium phosphate exists in the soil, and is taken up from it by plants. Animals consume phosphates in
rus.
.

343. Occurrence

and Preparation

their food.

Phosphorus is made from bone-ash, which is 60% to 70% Ca 3 (PO 4 ) 2 or from


,

The phosphates. is heated with phosphate


natural
charcoal

and

sand

in

an

electric furnace

(Fig. 78).

The charge

is

fed into a hopper,

and F, to prevent the escape of phosphorus while the charge is being


C, with trap bottoms,

put
the

The conveyor, G, forces Flf} 78 charge into the furnace. The heat for the reaction is developed by the resistance which the current encounters between the electrodes, A and B. The
in.

320
slag is

THE NITROGEN FAMILY.

drawn off through D. Phosphorus vapor escapes through Crude phosphorus is purified and is condensed under water. P, by redistillation. It is then pressed, while liquid (under water),
through a bone-ash
filter.

white, transparent solid.

The phosphorus thus obtained is a About 3,000 tons are made annually.
CaO) + (P 2 5 ). 3 CaSi0 3
.

The

partial equations for the reaction are,


(1)
(2) (3)

Ca3 (P0 4
(3

)2

(3

CaO) +3 Si0 2
5

(P 2

)+5C
2

2P+5CO.
3 CaSi0 3 +5

Hence the complete equation is,

Ca 3 (P0 4 ) 2 +3 Si0 +5 C

CO+2

P.

in

344. Properties. Phosphorus, like sulphur, exists several allotropic forms. Ordinary or yellow
specific

phosphorus has a
melts at about 45

gravity
boils at

of

about
C.

1.8,

C.,

and

287

It is

insoluble in water, but dissolves readily in carbon


disulphide,

CS

2.

It is

very poisonous.

" " Phosphorus derives its name, which means bearer of light from its of i. (cf. Latin, lucifer), property phosphorescing, e., glowing in the dark. This phenomenon is caused by slow combustion on the surface of the phosphorus. Ordinary phosphorus ignites in air at 40 C., and burns with a hot flame to phosphorus trioxide and pentoxide.

4P+30
4

2 2

P+5
(cf.

2P 2 PA2 3.

The spontaneous

ignition

of
31).

finely

divided phosphorus has

already been described

Phosphorus unites readily with chlorine, bromine, and iodine even at the ordinary temperature. Two compounds of phosphorus and chlorine are possible,
viz.,

the trichloride, PC1 3,

and

MOLECULAR WEIGHT OF PHOSPHORUS.


the pentachloride,

321
a liquid;

PC1 5 Phosphorus trichloride phosphorus pentachloride, a crystalline solid.


.

is

P+3 C1 P+5 C1

2 2

2 PC1 3 2 PC1 5

great difference exists between yellow phosphorus and the red modification. Red phosphorus is a reddish powder 2.2 times as
345.

Red Phosphorus.

heavy as water,

infusible at red heat, unable to in carbon disulphide, and insoluble phosphoresce, not poisonous. It ignites at about 260 C. in air. Red phosphorus unites with the halogens only when

heated.
prepared by heating the ordinary form in C. A small amount of the yellow phosremains phorus unchanged; this is removed by means of carbon disulphide, in which the red variety is insoluble.
is

Red phosphorus

closed iron tubes to, 300

a given amount of red phosphorus is burned, there is much less heat liberated than with an equal amount of the yellow form; the red has therefore much less energy than the yellow. This statement
agrees with the

When

known

fact that

when yellow phosis

phorus
of heat.

is

changed into the red there

an evolution

The Phosphorus. almost four is weight of a liter of phosphorus vapor times that of a liter of oxygen at the same temperature and pressure; consequently the molecular
346. Molecular

Weight

of

--

322

THE NITROGEN FAMILY.

-weight of phosphorus, as a vapor, must be about 124, that is, about four times the atomic weight. The molecular formula of phosphorus vapor is thus written

4,

just as that of

oxygen

is

2.

made

Most of the phosphorus that is 347. Matches. The ordinary friction is used to tip matches.

match, as made at present, consists of a splint of wood tipped, first, with sulphur, and then with a mixture containing some oxidizing agent, phosphorus, and an adhesive substance, like glue. The oxidizing agent may be potassium nitrate or chlorate,
or the oxide of lead

known

as red lead,

which has the

formula
The chemical
(1)

operations involved in lighting a


:

match

are

essentially as follows

The heat generated by rubbing the

tip of the

match

against a rough surface causes the phosphorus to combine with the oxygen of the oxidizing agent in immediate contact with it. (2) The combustion of the phosphorus causes the sulphur
to be raised to the kindling temperature of sulphur. (3) The burning of the sulphur raises the temperature of

the

wood

to the kindling point; and the match burns.

Safety matches have not the property of being

when rubbed; they require contact with a specially prepared surface. This surface is
easily ignited

usually on the side of the match box, and consists of red phosphorus mixed with sand. The tip of the
safety

match generally contains antimony trisulphide

(Sb 2 S 3 ), an oxidizing agent, and glue.

HYDROGEN PHOSPHIDE.

323

Hydrogen 348. Hydrogen Phosphide (PH 3 ). phosphide, or phosphine, is a colorless gas which, as
ordinarily made,
is

spontaneously combustible.

The

common method

a mixture of yellow phosphorus and a concentrated solution The equation is, of sodium hydroxide.
of preparing it is to heat

P+3 NaOH+3 H

NaH P0 +PH
2
2

3.

sodium hypophosphite.

FIG. 79.

(Fig. 79) consists of a generating flask conthe taining phosphorus and the sodium hydroxide solution. The flask has two holes, one for a tube from a hydrogen the of stopper

The apparatus

generator and the other for a delivery tube ending under water. The air of the apparatus is first washed out by means of hydrogen
(or illuminating gas)
;

the gas then cut

off,

and the

flask

is

heated.

The escaping phosphine may be


in the figure,

collected in a receiver, as

shown

exposed to the air, or the bubbles of the gas may be allowed to escape through the water directly into the air. The material of the white smoke formed when phosphine

and

this

burns

is

phosphorus pentoxide, water, and phosphoric acid.


is,

The equation for the combustion of phosphine


2

PH +4
3

PA+3 H 0,
2

324

THE NITROGEN FAMILY.

is not actually ignited until its reaches 100 C. As the gas is ordinarily temperature prepared, however, it contains small amounts of the

Pure phosphine

vapor which

another phosphide of hydrogen (P2H 4 spontaneously combustible, and which, therefore, ignites the phosphine.
of
is

),,

349.

Phosphonium

Salts.
,

3 garded as ammonia, by phosphorus; Although similar to ammonia in composition, phosphine is much less basic. The aqueous solution of phosphine is not alkaline at all; the compound PH 4 OH can hardly be present in the

NH

Phosphine may be rewith its nitrogen replaced

solution.

acids.

Phosphine can, however, be made to unite with the halogen The compounds thus formed correspond with the amhence, they are called phosphonium

monium salts of the halogens;


salts.

Phosphonium bromide
are
iodide
is

(PH 4 I)

(PH 4 Br) and phosphonium iodide much like ammonium bromide and iodide, respectively.
decomposed by soluble hydroxides,
is (cf.

Phosphonium

much

as

ammonium

chloride

203).

This fact

is

evident

from the equations,

NH C1+KOH PH I+KOH
4
4

> KC1+NH OH KI+PH +H,0.


4
3

(i.

e .,

NH +H 0);
3
2

350. Phosphides. --The phosphides of the metals may be considered derivatives of hydrogen phosphide, The just as sulphides are of hydrogen sulphide.

formula of calcium phosphide


phosphide,

is

Ca 3P2

of

silver

Ag P.
3

OXYGEN ACIDS OF PHOSPHORUS.

325

Calcium phosphide is a white solid; when it is treated with water or with hydrochloric acid, it gives off hydrogen phosphide. The equation resembles that for the action of hydrochloric
acid

upon ferrous sulphide

(c/.

253).

Ca 3P2 +6 HC1 Ca 3 P 2 +6 HOH


351
.

3 CaCl 2 +2 3

Ca(OH) 2 +2

PH PH
3.

3.

of

Oxides of Phosphorus. Two common oxides are phosphorus known, viz., the trioxide (P 2 O 3 ) and the pentoxide (P2O 5 ). Both are white solids.

The weight of a given volume of phosphorus trioxide in the gaseous state is known to be twice that demanded by the formula P 2 3 consequently it is better to write the formula P^.
;

Phosphorus pentoxide is formed when phosphorus burns in air or oxygen free from moisture.
4
It is a bulky,

P+5 O

PO
2

5.

white solid which has great attraction

for moisture; when put into water it hisses like hot iron. The first product is metaphosphoric acid,

HP0

3.

+H O
2

2HP0

3.

Phosphorus pentoxide has been referred to as capable of decomposing anhydrous nitric acid and producing nitrogen It is the anhydride of metaphosphoric 233). pentoxide (cf.
acid, as nitrogen pentoxide is of nitric acid.

Several comPhosphorus. and hydrogen pounds of phosphorus with oxygen are known. Three of these form a series like the
352.

Oxygen Acids

of

326

THE NITROGEN FAMILY.


(cf.

are,

oxygen acids of chlorine -

168 and 328)

they

Hypophosphorous Phosphorous add,


Phosphoric acid,

H PO H PO H PO
acid,
3 3 3
;

4.

353-

Hypophosphorous Acid.

Attention has

al-

ready been called to the fact that acts upon sodium hydroxide (cf. sodium hypophosphite (NaH 2 PO 2 ) With barium hydroxide, phine.
phite,

when phosphorus
348) it produces as well as phos-

barium hypophos-

Ba(H PO
2

2 )2,

is

produced.
are
salts

The hypophosphites
This
is

of

a monobasic acid

(cf.

166).

Its constitutional

hypophosphorous acid. formula is

H\

P/
,

N OH

only the hydrogen atom attached to oxygen being

by metals. Hypophosphorous acid is a powerful reducing to the ease with which it goes over into phosphoric
replaceable

agent,

owing

acid.

H P0 +0
3 2

H P0
3

4.

354. Phosphorous Acid. Phosphorous acid is an intermediate product in the oxidation of hypophosphorous acid. It is itself a reducing agent, owing to
its

ready oxidation to phosphoric acid. hydride is phosphorus trioxide, P 2 O 3


.

Its

an-

P2

+3 H

H P0
3

3.

PREPARATION OF PHOSPHORIC ACIDS.


Phosphorous acid

327

may

trichloride or tribromide

be prepared by treating phosphorus with water (c/. 321).


2

PCl 3 +3

is

HaPOa+3 HC1.
dibasic;
its

Ordinary phosphorous acid

structural formula

is,

therefore,

P OH.

/> \OH

355.

The Phosphoric

Acids.

The

three phos-

phoric acids are, (1) orthophosphoric acid, or simply phosphoric acid (H 3 PO 4 ); (2) pyrophosphoric acid

(H 4 P 2

7 ),

and

(3)

metaphosphoric acid

(HPO
is

3 ).

The anhydride

of all three phosphoric acids

05:

P 2 HP0 3 is P 2 H4 P is P 2
3 4

H P0
2

is

5, 5, 5,

3 2

H 0.
2 2

H 0. H 0.
2

minus one

Evidently, the molecule 2 0, and that of

H P 0?
4
2

is

HP0

is

two molecules of H 3P0 4 one of H 3 P0 4 minus one of

H 0.
2

Orthophosphoric acid
tional formula,

is tribasic,

as indicated

by the

constitu-

= P OH.

/ OH
\)H

The 356. Preparation of the Phosphoric Acids. acid is to red treat obtain best way to orthophosphoric
phosphorus with
nitric acid,

and to evaporate the

At the ordinary temperature the resulting solution. acid consists of colorless, deliquescent crystals.

328

THE NITROGEN FAMILY.

Pyrophosphoric acid is best made by heating the or/Ao-acid some time to 260 C.; the meta- acid is made by heating the ortho- or the pyro- acid to 300 C.
for

Metaphosphoric acid always results oxide dissolves in water.

when phosphorus pent3.

P
When
ortho- acid.

+H
3

HP0

the meta- acid

is

boiled with water


>

it

goes over into the

HP0 +H

H P0
3

357. Phosphates. Phosphoric acid acid salts and a normal salt (cf. 164)
:

forms

two

(1)

(2)

(3)

NaH P04 is sodium di-hydrogen phosphate. Na HP0 is di-sodium hydrogen phosphate. Na P0 is tri-sodium phosphate.
2

Salts like the

first,

in

which one-third
called

of the hydro-

gen

replaced, those like the second


salts

is

are

primary

phosphates;

are

secondary phosphates.

The normal
corresponding
2

are

tertiary

calcium
4,

salts
3

have
4

The phosphates. the formulas


respectively.

Ca(H PO ) CaHPO and Ca (P0 )2, The common sodium phosphate of


4 2,

is

Na2HPO
184).

4.

It is

The

"

acid

the laboratory slightly alkaline to litmus (cf. "

sodium phosphate
is

is

NaH P0
2

4.

obtained by evaporata solution the ing containing ordinary phosphate and sodium hydroxide. In solution it is hydrolyzed:

Normal sodium phosphate

Na HP04 +NaOH
2

7
is

Na P04 +H 0.
3 2

When

a primary phosphate

heated, a metaphosphate results:

NaH P0
2

NaP03 +H 0.
2

USES OF THE PHOSPHATES.

329

secondary phosphate gives a pyrophosphate when heated:


2

Na HP04
2

Na P
4

+H 0.
2

A tertiary phosphate is not decomposed by heating.


either
is made by heating sodium di-hydrogen phosphate or sodium ammonium hydrogem phosphate upon a loop of platinum wire. Sodium ammonium hydrogen phosphate (also called " microcosmic

The

so-called

"

metaphosphate bead

"

salt ")

has the formula

NaNH HP0
4

4.

When
a

heated
"
fixed

it

first

loses

ammonia, like any ammonium giving sodium di-hydrogen phosphate.

salt of

"
acid,

This then loses water.


3

NaNH HP0
4

NaP0 3 +NH

+H 0.
2

reacts with the oxides of metals, forming mixed orthophosphates. Some of these have characteristic colors, and are used as tests for the metals.

Sodium metaphosphate

CoO+NaP0
358.

>

CoNaP0

4.

Uses

found

in bone-ash

of the Phosphates. --The phosphate and in phosphate rocks is normal

calcium phosphate, water. To convert

Ca 3 (PO 4 )2.
it

This

is

insoluble in

into soluble form for the use

of plants it is treated

changes
soluble.

it

with sulphuric acid. This into the primary phosphate, which is

Caa(P0 4 ) 2 +2

H S0
2

2
is

CaS0 4 +Ca(H P0 4 )
2

2.

The primary phosphate


phosphate";
sulphate
is

commonly known

as

"

soluble

the mixture of the primary salt and calcium


"

is

called

superphosphate."

The primary phosphate

" acid phosphate baking powders (cf. 280). To be fertile, soil must Prosphates Necessary for Plants. an essential calcium contain plant food. When the phosphate,
also used in

"

crops are removed, part of the phosphate of that region goes

330

THE NITROGEN FAMILY.

land

with them; hence, phosphate must be returned to the soil if the is to yield good harvests. If the crops are used as food for

if

animals, part of the phosphate returns to the soil in manure; Nature usually keeps a not, other fertilizers must be used.
soil

soil fertile

the

"

by means of decaying vegetation, which forms with vegetable mould."

Fertilizers.
gen,

complete fertilizer supplies potassium, nitrofertilizers,

and phosphorus. Most one or two of these essentials.


Potassium
is

however, contain only

carbonate (wood-ashes;

usually returned to the soil as the sulphate or cf. 420); sometimes as chloride.

Nitrogen

is

frequently supplied as

ammonium
418).

salts,

or as
is

nitrates, especially

sodium

nitrate (cf.

Nitrogen

also

contained in guano. " soluble Phosphorus is contained in fertilizers chiefly as phosphate," which is obtained by treating phosphate rocks or

bone-ash with sulphuric acid.

The dry
houses,
fat, oil.
e. g.,

residue left after the waste products of slaughtertainted meat, bones, hoofs, etc., are deprived of
gelatine,

and

makes a good

fertilizer.

The

fat is used

as soap-stock.

B.

Arsenic.

359. Occurrence and Preparation of Arsenic. The element arsenic is found in nature both free and
combined. Its chief ores are realgar and orpiment (As 2 S 2 and As 2 S 3 respectively), the oxide (As 2 O 3 ),
,

and

arsenopyrite

(FeAsS).

Arsenopyrite

is

iron

pyrites (FeS 2 ) with half of the sulphur replaced


arsenic.

by

The element may be prepared by reducing the


oxide with charcoal.

2 As-f 3 CO.

PROPERTIES OF ARSENIC.
360. Properties of Arsenic.

331

Arsenic forms comwith the compounds which correspond closely pounds The element itself is, however, of phosphorus. more metallic than phosphorus. It exists in at
least two allotropic forms. The ordinary form of arsenic is gray,
line structure,

has a crystalabout 5.7 times as heavy as water. It is not at all malleable, but, on the contrary, crumbles to powder when struck.

and

is

When
the

arsenic

air, it

heated to about 500 C. out of contact with sublimes, forming a yellow vapor. By comparing the
is

weight of a known volume of this vapor with that of oxygen under the same conditions, it is found that the molecular weight of arsenic is about 300. The atomic weight being 75, the molecule must contain four atoms; hence, the molecular formula
is

As4.

Above 1700

C.,

however, most of the molecules con-

taining four atoms dissociate into simpler molecules of two atoms each, i. e., As 2 molecules.

arsenic trioxide,

Arsenic begins to burn at about 180 C. to form The flame is bluish-white. As2O 3
.

Like phosphorus and antimony, arsenic unites with chlorine at the ordinary temperature to form the
chloride,

AsCl 3
2

As+3

C1 2

2 AsCl 3

The same substance is formed when arsenic trioxide, As 3 is treated with concentrated hydrochloric acid
2
,

solution.

HC1

2 AsCl 3 +3

H O.
2

332

THE NITROGEN FAMILY.


;

it is decomis a colorless liquid arsenious acid of excess an water, giving posed by and hydrochloric acid.

Arsenic trichloride

/Cl

HOH

As-Cl+HOH

- As-OH+3 HCL
/OH
is

HOH
Arsenic trichloride
ride,

thus like phosphorus trichlo354).

which with water gives phosphorous acid and


(cf.

hydrochloric acid

361.

Hydrogen Arsenide.

Arsenic combines with

nascent hydrogen to form hydrogen arsenide or arsine, AsH 3 a substance which corresponds with phosphine
,

Arsine cannot, however, be made to unite 3 with hydrobromic acid, etc., to give compounds resembling ammonium and phosphonium salts (cf.
gas,
.

PH

349).

The most common method

of

getting

arsine

(mixed with hydrogen) is to add an arsenic compound to a flask in which hydrogen is being generated; the nascent hydrogen unites with the arsenic of the

compound.
Marsh's Test.
Advantage
is

taken of the properties of

arsine to test for the presence of arsenic in test is known as Marsh's test.

any substance; the

80), there is attached

is being generated (Fig. a calcium chloride tube and a hard glass tube drawn out as shown in the figure. The hydrogen is allowed to pass off until the usual test (cf. 50) shows that all air has

To a

flask in

which pure hydrogen

ARSENIC TRIOXIDE.

333

FIG.

80.

The jet of hydrogen is now lighted, and a few of the drops liquid to be tested for arsenic are added through
been removed.
If arsenic is present, the flame changes to a bluish-white color, and a cold piece of porcelain held in the flame " receives a shiny, black deposit, called an arsenic mirror."

the thistle-tube.

it

the hard glass tube is heated, the arsine passing through decomposed, and an arsenic mirror appears in the tube. Here the arsenic may be identified by passing hydrogen sulphide,
If
is

The same precautions must be 2 S, through the heated tube. taken to have all air removed as in the case of hydrogen. HyAs 2 S 3
drogen sulphide changes the arsenic into arsenic trisulphide, this is a golden-yellow solid called orpiment (from auri
;

pigmentuni). If, now, dry hydrochloric acid gas is passed through the tube, the arsenic trisulphide does not change. These properties serve to distinguish between the arsenic mirror and

that of antimony

(cf.

369).

362. Arsenic Trioxide. --The oxides of arsenic are the trioxide (A^Os) and the pentoxide (As2 05); these correspond to the phosphorus oxides. Arsenic " " " trioxide (often called or arsenic white arsenic ")

334
is

THE NITROGEN FAMILY.

It is a without white powder which sublimes, melting, at about 220 C. The vapor has a garlic odor. When

the most

common

arsenic

compound.

the vapor solidifies, the arsenic trioxide appears in the form of a transparent mass. At very high temperatures the molecule of the vapor is represented

by As2
Uses.

cules are doubled,

but between 220 and 700 C. the moleand the formula is As^Oe. Arsenic trioxide is used in medicine and

Its poisonous action upon the human as a poison. system is rather slow, because it dissolves only

is

slowly in the liquid of the stomach. The antidote a mixture of ferric hydroxide [Fe(OH) 3 ] and

magnesia (MgO).
The people of certain mountain districts are addicted to the use of arsenic trioxide because it enables them to breathe more
easily
ties

when

climbing.

By

beginning with very small quanti-

and gradually increasing the dose, they are able to take much more than the lethal dose without injury. But the difficulty comes when they try to leave off the habit; for they then
suffer all the effects of arsenic poisoning.

Arsenic trioxide is slightly 363. Arsenious Acid. soluble in water; the solution probably contains arsenious acid, 3 AsO 3

As2O 3 +3
Arsenious acid
it is

HO
2

>

H As0
3

3.

not

known

in the free state because


(its

breaks up into arsenic trioxide

anhydride) and

water.

The

salts of arsenious acid are called arsen-

ARSENIOUS ACID.
ites.

335

Solutions of these are formed


is

when

arsenic

Thus, hydroxide and arsenic trioxide (with water this arsenious acid) form sodium arsenite, Na 3 As0 3
.

trioxide

treated

with

alkalies.

sodium
is

H As0 +3 NaOH
3 3

Na As0 +3 H
3 3

O.
,

which

Many arsenites are derived from metarsenious acid, HAs0 2 may be looked upon as arsenious acid minus water. HAs0 +H20. HsAsOs
2

Sodium

metarsenite

would be

NaAs0 2

Double Nature

of Arsenious Acid.

Arsenic

tri-

oxide (or arsenious acid) reacts not only with alkalies, giving arsenites and water, but also with acids, giving arsenic salts and water. Thus, with con-

centrated hydrochloric

acid

we

get arsenic trichloride

and arsenic and water.

trioxide,

As2
3

+6 HC1 H AsO +3 HC1


3

2 AsCl 3 +3

AsCl 3 +3

H O; H O.
2 2

or,

Arsenious acid has thus a double nature; for toward strong bases it acts like an acid, forming with the base an arsenite; while toward a strong acid it acts
like

a base, giving with the acid a


is,

Arsenic

in fact,

and water. intermediate between the nonsalt

metals and the metals.


Arsenic Greens.

At

least

two arsenic compounds have


"

Scheele's a bright green color; these are copper arsenite, called and arsenite of mixture and a copper acetate, copper green,"
called

"

Schweinfurt's green."

Both

of these are sold as

"

Paris

336
green."
paints,

THE NITROGEN FAMILY.


These dyes were formerly used to color wall-paper, They are too dangerous, however, and are now
Paris green
is

etc.

rarely used as dyes.


etc.

used to destroy potato-bugs,

is

Arsenic 364. Arsenic Acid. of arsenic the anhydride acid,

pentoxide,
3

As2 O 5

As2
Arsenic

+3 H O
2

H As0 2 H AsO
4
.

4.

acid is formed by dissolving arsenic or arsenic trioxide in concentrated nitric acid. (Com-

pare the preparation of phosphoric acid from phosThe arsenic acids have formulas 356.) phorus,
of the

same type as those

of

phosphorus

H As04
3

is
7

orthoarsenic acid;

H4As 2

is

HAs0
2

is

pyroarsenic acid; metarsenic acid.

Metarsenic acid finally gives, by loss of water, arsenic pentoxide.

HAs0

H 0+As
2

5.

The
phates.

arsenates

are like the corresponding phos-

of

When the solution 365. Arsenic Trisulphide. an arsenic compound is treated with hydrogen

sulphide, a yellow precipitate is generally produced; this consists of either the trisulphide (As 2 S 3 ) or the

pentasulphide

ammonium
sulphides.

Both sulphides react -with sulphide [(NH 4 ) 2 S] and other soluble


(As2 S 5 ).
solution

The

contains

sulpharsenite

PREPARATION OF ANTIMONY.

337

or sulphar senate. Thus with sodium sulphide and arsenic trisulphide the equation is, -

Na^S+AsA

Na AsS
3

3.

with

The sulphar senite (Na3 AsS 3 ) is simply an its oxygen replaced by sulphur.

arsenite

When the sulpharsenite is treated with a dilute acid, e. g., hydrochloric acid, sulphar senious acid, HsAsSs, is set free; this breaks up into hydrogen sulphide and arsenic trisulphide. These Arsenic trisulphide, being insoluble, is reprecipitated.
facts are

shown
3

in the equations,
3

Na AsS +3 HC1
2

>

HsAsSs+3 NaCl.
3

H AsS
3

H S+As S
2

3.

Ammonium

sulpharsenite,

(NH 3AsS
4)

3,

undergoes

similar

decomposition.

C.

Antimony.

366. Preparation of Antimony. Antimony is found in nature chiefly combined with sulphur in the mineral stibnite, Sb 2 S 3 To obtain the element the sulphide is first roasted, i. e., heated in a stream of air, and then heated with charcoal.
.

Roasting converts the antimony sulphide into the


(Sb 2
3 ),

trioxide

or the tetroxide (Sb 2

4 ),

and sulphur
2 Sb 2
3

dioxide.
2
;

2 Sb 2 S 3 +9

2 2

Sb 2 S 3 +5

>

Sb 2

+6 S0 +3 S0
2.

or,

The reduction of either of these mony and carbon monoxide.


SbiOa+3 C

oxides

by charcoal

gives anti-

Sb+3 CO.

338

THE NITROGEN FAMILY.

367. Physical Properties. Antimony is a solid having a bright, silvery luster which is not easily tarnished in air. Antimony is not malleable. At about 430 C. it melts to a liquid of a slightly higher When melted antimony solidifies specific gravity. it expands again; hence antimony is valuable as a constituent of materials for casts, such as type-metal.

The

specific gravity of the solid is 6.7.

The

specific

gravity of the vapor shows that in the gaseous condition the formula of the molecule is Sb 2 (cf. 346

and 360).

368. Chemical Properties. Antimony burns in the air to form the trioxide or the tetroxide. It

combines with chlorine to give antimony trichloride With fluorine, 118) or the pentachloride, SbC^. (cf. bromine, and iodine it forms similar compounds.

Antimony is
acid oxidizes
acid,

it

H SbO4.
3

insoluble in hydrochloric acid. Nitric to antimony trioxide or antimonic

4Sb+30
4

2 2

2Sb 2
2
2

3.
5. 3

Sb+5
5

Sb 2
2

Sb 2

+3 H

H Sb0

4.

With aqua
trichloride.

regia

antimony

reacts, giving
is

antimony

When

the solution

distilled it gives

the trichloride as a liquid boiling at 223 C. This " solidifies to a pasty mass called butter of anti-

mony."

CHEMICAL PROPERTIES.

339

Concentrated sulphuric acid reacts with antimony. The products are shown in the equation,
2

Sb+6

H S0
2

Sb 2 (S0 4 ) 3 +3 H^SOa+S antimony sulphate

H 0.
2

the one

Antimony resembles arsenic and phosphorus on hand and bismuth on the other. It is like

the former elements in the general structure of its compounds; like the latter in its ability to form a
salt

with sulphuric acid and in other metallic prop-

erties.

Its positive

(+) properties

are,

however, weak,
of its

as

is

indicated

by the easy decomposition

salts

by water.
is

Thus, antimony trichloride


giving a basic chloride drochloric acid.
(its

simplest formula

decomposed by much water, is SbOCl) and hy-

Cl

HOH

Sb

Cl+HOH
Cl

Sb

OH OH
Cl

Sb

OH OH+2 HC1.
Cl

SbOCl+H 20.

Again, although antimony trioxide reacts with concentrated


sulphuric acid, giving antimony sulphate, Sb 2 (S0 4 )3, yet when antimony trioxide reacts with the dilute acid, the product has

the formula (SbO) 2S0 4

The compound SbOCl may be


chloride,

called

antimony oxy-chloride or antimonyl


being called antimonyl.

The

the group SbO compound having the formula

(SbO) 2S04

is,

therefore, antimonyl sulphate,

340

THE NITROGEN FAMILY.

Antimony, even more than arsenic, is a transition reacts not only with Its oxide, Sb 2 O 3 acids, giving antimony salts, but also with alkalies,
element.
,

antimony acids. Thus, antimony sodium hydroxide sodium antiThis is a salt of antimonious monite, NasSbOs. which with acid, corresponds phosphorous and
giving
salts

of

trioxide gives with

arsenious acids.

369. Other

Antimony Compounds.

Among

the

important antimony compounds are hydrogen antimonide (or stibine), tartar emetic, and antimony
trisulphide.

Hydrogen antimonide, SbH 3 is formed from an antimony compound just as hydrogen arsenide is formed from an arsenic compound, namely, by reduction with nascent hydrogen (cf. 361).
,

Marsh's test

may be

carried out with

antimony

in the appara-

tus used for arsenic (Fig. 80). When, however, hydrogen sulphide is passed over the antimony mirror, the antimony sulphide

Again, when passed through the tube, the antimony sulphide forms drops of antimony trichloride, while the arsenic We can thus distinguish between trisulphide is unchanged.
is

formed

black, while that of arsenic is yellow.


is

hydrochloric acid gas

arsenic

and antimony.

Tartar
of

emetic
6.

is

K.SbO.C 4 H 4
antimony

potassium

antimonyl

tartrate,

It is

trioxide,

formed by heating a mixture potassium hydrogen tartrate


It is

(cream of tartar), and water.

used in medicine.

PREPARATION OF BISMUTH.

341

Antimony trisulphide, Sb 2 S 3 , is formed by treating solutions of either antimonious salts or antimonites


with hydrogen sulphide.
trisulphides are
cipitation
is

Two

isomeric antimony
pre-

known.

The one formed by

red form

is

brick-red, while stibnite is black. unstable; it goes over into the black

The
form

with evolution of heat.

The precipitate of antimony trisulphide reacts readily with alkaline sulphides giving sulphantimonites, just as arsenic trisulphide gives sulpharsenites (cf. are decomposed by dilute acids;
reprecipitated.
365).

The sulphantimonites
trisulphide
is

and antimony

370.

Uses

of

Antimony.

Antimony
are:

is

used in

making
metal,

Examples alloys. typepewter, and Britannia metal. Antimony black is a finely divided form of the metal; plaster casts are rubbed with it to give them a metallic
D.
Bismuth.

Printer's

coating.

in nature free

Bismuth is found 371. Preparation of Bismuth. and also in the form of the sulphide It is prepared from (Bi 2 S 3 ) and the oxide (Bi 2 3 ).

sulphide as antimony is, namely, by first roasting the sulphide to form the oxide, and then reducing the oxide.
its

it is

get bismuth free from impurities, such as arsenic, etc., mixed with saltpeter and heated. The impurities are thus oxidized to compounds soluble in water, and can be separated from the bismuth.

To

342

THE NITROGEN FAMILY.


physical appearance bisantimony, but it has a slightly
its

372. Properties.

In

muth
and
C.

is

much

like

reddish color.
its specific

Its melting

temperature is 265 C., gravity about 10. It boils at 1700


in the air

Bismuth burns
product
is

when
.

at red heat;

the

the trioxide, Bi2 O 3


trioxide
230),
is

Bismuth

Bi(N0 3 ) 3

(see

formed, also, by heating the nitrate and by heating the hydroxides Bi(OH) 3

and BiO.OH, which are produced when potassium hydroxide solution is added to a solution of a bismuth salt.

Unlike the trioxides of arsenic and antimony, bismuth trioxide has not the ability to react with It is an entirely basic oxide. alkalies to form salts. The higher oxide of bismuth, Bi2 5 has slightly
,

acidic properties; for


acid,

it is

the anhydride of bismuthic

HBiOs.

The

acid

is,

however, very weak and

very unstable.

Bismuth forms no hydrogen compound corresponding to ammonia, phosphine, arsine, and stibine. Bismuth combines with 373. Bismuth Salts. the halogens, giving tri-halogen compounds, which correspond to those of arsenic and antimony. It
reacts with nitric acid to give the nitrate, with aqua regia to give the chloride, BiCl 3

Bi(N0 3 ) 3
,

and with

concentrated sulphuric acid to give the sulphate,

Bi2 (S0 4 ) 3

THE NITROGEN FAMILY.


Bismuth
salts,

343

like those of
salt

antimony, are decomposed by

much

water, giving the basic

and

free acid.

The

trichloride

usually decomposes as follows:

Cl

HOH
>

Bi

Cl+HOH
Cl

Bi

OH OH+2 HC1.
Cl

Bi(OH) 2 Cl

BiO.Cl+H 2O.

The

nitrate

decomposes in a similar way.

When
of a

hydrogen sulphide
salt there is

bismuth

added to the solution produced an almost black


is

precipitate of bismuth sulphide, insoluble in alkaline sulphides.

Bi2 S 3

This

is

Uses of Bismuth. - The principal use of bismuth is as an ingredient of alloys. Its chief alloys are Wood's metal and Rose's metal. Wood's metal consists of four parts, by weight, of bismuth, one each of tin and cadmium, and two
374.
It melts at about 65 C.; hence it is much used for metal baths in the laboratory. Rose's metal contains nine parts of bismuth to one each of lead and tin; it melts at 94 C.

of lead.

The

basic nitrate of

bismuth (simplest formula, BiO.NOs)

is

used in medicine under the

name bismuth

sub-nitrate.

375.

The Nitrogen Family.

The elements

nitro-

gen, phosphorus, arsenic, together with some rare

antimony, and bismuth, elements, form a natural

family, just as the halogens do; for in this, the nitrogen family, just as in the case of the halogens,

344

THE NITROGEN FAMILY.


series of

we have a

elements exhibiting a gradation

of properties in the order of the atomic weights. The table on the next page shows this for some

properties.

complete

list

of the properties of the

members

of the nitrogen family will not agree so well as in the case of the halogens. When, however, we can com-

pare

corresponding
of

number

compounds having the same atoms to the molecule, a fair degree of

regularity exists.

376. Exercises.
1.

What means

are there of kindling

fires

without the use of

phosphorus?
2.

How much

phosphorus
if

is

there in 440 grams (about one

pound) 3. Express the hydrolysis

of bone-ash,

70%

of the ash is
of

Ca 3 (P0 4 ) 2 ?

by equilibrium equations. presence of much or little acid? Much or get the basic chlorides into solution?

antimony and bismuth chlorides Would hydrolysis be favored by the


little

water?

How

4. Write the formulas of the following substances: normal barium phosphate, primary ammonium phosphate, potassium

hypophosphite,
phate.

strontium

metaphosphate,

and

silver

pyrophos-

5. Why is it undesirable that arsenic compounds should be used to color wall papers? Explain. 6. Show by an equation the reduction of arsenic trioxide by

nascent hydrogen to arsine. The combustion of arsine. 7. When a bath of Wood's metal is being melted the un-

melted metal

floats

upon the

liquid portion.

Compare the
Will the

specific gravity of the solid

with that of the liquid.

liquid expand or contract on solidifying?

EXERCISES.

345

ELEMENT.

CHAPTER

XXVII.

THE PERIODIC SYSTEM.


377. Natural Families. During the first half of the nineteenth century various attempts were made
to classify the elements. Chemists recognized the " " of elements, fact that there were natural families

and that the members


homologous

of the

same family

(called

elements), bearing a general resemblance to one another, yet showed a regular gradation of properties in the order of the atomic

while

weights.

We
viz.,

have already described two


(cf.
(cf.

of these families,

the halogen family


375).

335) and the nitrogen

family

Other natural families exist. Thus, sulphur and oxygen, with the rarer elements selenium (Se) and tellurium (Te) form a group of homologous elements. The atomic weights are,
0, 16; S, 32; Se, 79; Te, 127.

Again, the elements lithium, sodium, and potassium, with , the rare elements rubidium and caesium, form the well-known

"alkali" group of metals.

The atomic weights


Na, 23; K,
39.

of the three

more common metals

of the family are,


Li, 7;

Here, as in the case of the halogens, we find a continuous gradation of properties in the order of the atomic weights.
346

THE PERIODIC ARRANGEMENT.

347

Lithium hydroxide, LiOH, is a weaker base than sodium hywhile potassium hydroxide, KOH, is the droxide, NaOH;
strongest base of the three.

378. The Periodic Arrangement. Although the connection between the properties and the atomic weights of elements in the same group had been recognized for years, it was left to the Russian

chemist Mendelejeff and the German chemist Lothar Meyer to discover, in 1869 to 1871, a new and peculiar relation between the properties of all elements and
their atomic weights.

This relation

is

the basis of

the Periodic System. Let us write the symbols of the

first sixteen ele-

ments in
related,

atomic weights. Omitting hydrogen, which for the present stands almost unthe order of the

we have, Li 7
Si

Element,

Atomic Wt.,
Element,

Gl(Be) 9

B
11

C
12

N
14 16

F Na Mg
19

Al
27

23

24

P
31

Atomic Wt., 28

S Cl 32 35.5 39

Ca. 40

study of the elements from lithium to fluorine, inclusive, shows that there is a regular gradation of
properties. lithium are
boron.

The

strongly
of

metallic

properties

of in

weaker

in glucinum,

and yet weaker

The hydroxide
acid.

boric

boron is, in fact, called In carbon we have an element with


i.

faintly electro-negative,

e.,

non-metallic, properties;
still

the

elements nitrogen and oxygen are


until in fluorine

more

electro-negative;

we have

a typical

348

THE PERIODIC SYSTEM.

non-metal, and probably the most electro-negative substance known.


increase of atomic weight from 7 to 19 has thus continudiminished the electro-positive, or metallic, character ously possessed by lithium, and has increased the electro-negative

The

character typified

by

fluorine.

But after fluorine the gradation of properties does not continue; for the element sodium, the next greater in atomic weight, is, like lithium, one of the
most typical
"
metals.

There

is,

in fact,

a sudden

reversion to type"; for sodium belongs in the same natural family with lithium.

atomic weight, writing the second set of seven elements under the first Sodium will be under 379. set, as in the table in

Let

us, then, proceed in the order of

find magnesium under glucinum, etc. the same gradation of properties with increase of atomic weight from sodium to chlorine as we found

lithium

We

from lithium to fluorine.


Magnesium, like sodium, is a metal; but magnesium hydroxis a weaker base than sodium hydroxide. Aluminum, the next in the order of atomic weight, is also metallic; but its hydroxide is either a base or an acid, according to circumstances.
ide

In

silicon,

the next element, metallic properties are wanting;

silicon

silicic acid. Next come phosphorus and sulphur, undoubted non-metals; and then chlorine, the first homologue

forms

of fluorine.

The element
its

following
is

chlorine

is

atomic weight

39.

Potassium

is

potassium; a typical

PERIODIC ARRANGEMENT.
metal, and belongs in the

349

same family with lithium In passing from chlorine to potassium we have, therefore, a second instance of " reversion
and sodium.
to type."

The properties of calcium are less metallic in character than those of potassium; for calcium hydroxide is a weaker base
than potassium hydroxide. Thus, after potassium, as after sodium, variation in the properties of the elements goes on continuously with increase of atomic weight for another period.

From

the study of

"

natural families

"

we

learned

that the properties of the elements in any one family vary continuously with the atomic weight; now we
see that the properties of all elements, while not varying continuously, as in the natural family, yet

vary periodically with the atomic weight. That is to say, a certain increase of atomic weight is accompanied by a recurrence of certain properties possessed by an element of lower atomic weight.

The

facts are

summed up
"

in

what

is

often called the


1

Periodic Law, which

of the elements is, ' are periodic functions of their atomic weights.

The properties

If

379. Regularities in the Periodic Arrangement. we write down the symbols of the elements from
vertical
:

lithium to calcium, putting similar elements in the

same
Li
(7)

columns,

we have an arrangement
(11)

like

the following

Gl or Be

(9)

(12)

N (14)
P
(31)

(16) Fl (19)

Na

(23)
(39)

Mg
Ca

(24)

Al (27) Si (28)

(32)

Cl (35.5)

(40)

350

THE PERIODIC SYSTEM.


:

In this table we observe several regularities


(1)

After every period of seven elements a second period of

seven begins.
(2)

The

difference

between the
etc.,

first
is

second and the ninth,


teen units.

elements

and the eighth, the in every case nearly six-

Two successive elements of the same family are thus separated by six intervening elements, and differ from each other by about sixteen units of atomic weight.
i.

Elements in adjacent positions in the horizontal rows, e., heterologous elements, differ from one another by small numbers of units, generally only one or two. The largest differences occur between fluorine arid sodium and between chlorine and potassium, i. e., at the break in the periods.
(3)

We may

380. Properties call the

of an Element Determined. two elements adjacent to another

element in the horizontal rows the adjacent heteroThus, boron and nitrogen logues of the element.
are the adjacent heterologues of carbon. The two adjacent heterologues and the two adjacent homologues of an element may be called the analogues of the element. Thus, glucinum, sodium, calcium,

and aluminum are the analogues of magnesium. Mendelejeff showed that if the properties

of

magnesium were wholly unknown they could be deduced approximately from the properties of its
four analogues.
Thus, the atomic weight of magnesium (24) average of the atomic weights of its analogues.
is

very nearly the

"

GAPS " IN PERIODIC ARRANGEMENT.

351

magnesium
sium

Again, the average of the specific gravities of the analogues of gives approximately the specific gravity of magneitself.

The specific gravities of sodium, aluminum, gluand are 0.97, 2.56, 2.10, and 1.58, respectively. calcium cinum, The average is 1.8. Experiment shows the specific gravity of magnesium to be 1.75. Up to the time of Mendelejeff and Meyer, the existence of an element with any particular properties was regarded as an isolated and accidental fact in nature; but the periodic arrangement presents the idea that it is necessary that elements of given atomic weight shall have certain definite properties.
381.

When

" in the Periodic Arrangement. Mendelejeff first drew up his table of the

"

Gaps

elements, he found that in several cases neighboring heterologous elements did not fall into place, i. e.,
into the vertical rows containing the other
of their natural families.
(65)

members

Thus, the element zinc

was followed by
family

large, viz., ten units.

The interval is arsenic (75). Now, zinc belongs in the same

magnesium; and if arsenic must belong to the family of Hence the second and fourth horizontal rows would be as follows 2. Na (23) Mg (24) Al (27) Si (28) P (31) S (32) Cl (35.5)
natural

with

follows zinc, arsenic boron and aluminum.

4.

Cu(63)

Zn

(65)

As

(75)

Se(79)

Br(80),etc.

This arrangement is manifestly impossible; for by all its properties bromine belongs with chlorine, selenium with sulphur, and arsenic with phosphorus. The arrangement of the second and fourth rows
should be,

352
2.

THE PERIODIC SYSTEM.


Al
(27)

4.

Na (23) Mg (24) Cu (63) Zn (65)

Si (28)

P
As

(31)

(32)

Cl (35.5)

(75)

Se (79)

Br

(80)

There were, therefore, two gaps in the fourth row; a member of the aluminum family and a member of the silicon family were wanting.
Reason382. Prediction of Unknown Elements. from the the that properties of an ing assumption
element are determined by its position in the periodic grouping, Mendelejeff drew up a table stating the properties of the unknown elements that ought to
fill the gaps in the fourth row. The suphe called element of the aluminum posed family ek-aluminum, and that of the silicon family, ekasilicon. Another gap existed in the third row, between calcium (40) and titanium (48). To this element Mendelejeff gave the provisional name eka-

exist to

boron.
1871.

Mendelejeff and Meyer's tables were published in Four years afterward an element having the

properties of ek-aluminum

was discovered

and named Gallium.


to be 70, as predicted.

Its

in France, atomic weight was found

In 1880, Nilson and Cleve discovered in a Scandinavian mineral a new element which had the properties of eka-boron. They called it Scandium. In 1886, Clemens Winkler discovered the element which he called Germanium. Upon comparing the properties of this element (atomic weight 72) with those foretold for eka-silicon, he decided that the

CONCLUSION.

353
else

new element could be nothing silicon predicted by Mendelejeff

than the eka-

fifteen years before.

Other elements, more recently discovered, have also been found places in the periodic table. Thus radium (at. wt. 226.4) fills the space below mercury.

383.

The Periodic Table.


is

periodic table clude the Zero group,

The

given on the following page.


groups.

we have nine

If we inThe group marked

VIII consists of three sub-groups of three elements each. These do not fit into the table elsewhere. Each sub-group consists In osmic acid anhydride, OsO,*, we of closely related elements.

have an element with a valence of

8.

Group IV reach the highest valence toward hydrogen, i. e., 4. From Group IV to Group VII the valence toward hydrogen decreases. The valence of the elements toward

The elements

of

oxygen increases from Group

I to

Group VIII.

R is a general symbol for all the elements.


The Argon Family. The discovery of the Argon family new group, the Zero Group, into the
384.
of this group are all

192) introduced a (cf. Helium periodic table.

comes before lithium; neon before sodium, etc. The elements monatomic (cf. 142), and their valence is,

apparently, zero.

Besides resulting in the preundiscovered elements, the periodic classification has led to a more careful study of the atomic weights of known elements.
385. Conclusion.
diction of the properties of

has many faults, but it is full of suggestions, and shows a striking relationship between
classification

The

354
.

THE PERIODIC SYSTEM.


o

EXERCISES.
the elements.

355

Because of this relationship chemists

are tending to the belief that all the elements are modifications of some yet simpler forms or form of matter. As to the character of this fundamental
substance, nothing is known at present. irregularity in the periodic arrangement

recent
results

from the fact that the atomic weight of tellurium has been placed at 127.5, or slightly higher than iodine, 126.9, and that argon (39.88) comes before
potassium
for
(39.10).

This

is

not startling, however,


is

the periodic recurrence of properties approximate, at the best.


386. Exercises.
1.

only

The

specific

gravities
(liquid),

of

some elements are as


Cd,
8.6;

follows:

(red),

2.14;

Cl

1.33;

In, 7.4;

Using these figures and those in Appendix v, see if relation between specific gravity and atomic weight in Series 3 (begin with Na), and in Series 7.

Te, 6.2. there is a

2. Three elements that appear upon the list of International Atomic Weights, but are not in the periodic table, are dysprosium (Dy=162.5), europium (Eu=152), and lutecium (Lu = 174). Are there places for them? Is the existence of a blank in the

proper place the only condition necessary for placing elements in


particular groups?

what
will

dysprosium belongs where its atomic weight places it, the formula of its oxide, chloride, and nitrate? If europium belongs in a blank, according to its atomic weight, what
3. If
is

be the formulas of

its

hydroxide,

carbonate,

sulphide,

sulphate,

6,

and nitrate? Answer the same questions for lutecium. 4. What two kinds of elements might fill the blank in Series Group VII? What atomic weight belongs in this space?

CHAPTER
SILICON
A.

XXVIII.

AND BORON.
Silicon.

As was stated in 387. Occurrence of Silicon. 9, silicon is, next to oxygen, the most abundant
constituent of the earth's crust.

but in the form of


i.

its oxide,

It is not found free, SiO 2 and in silicates,


,

e.,

the salts of

silicic acid.

Silicon dioxide (silica)


all

and the

silicates make up sand, clay, and almost the crystalline rocks of the earth's crust.
Silica is

taken up by plants.
it.

grains contain from the large


also, in

The straw and husks of the The equisetum is called " scouring-rush," amount of silica present in it. Silica is found,
nails, hair, etc., of

the skin,

animals.

Certain microscopic plants, the diatoms, have skeletons of silica; and these have accumulated in large deposits in some
places.

Silicon, like carbon, exists in 388. Preparation. The amorphous variety several allotropic forms.

may

be obtained by heating a mixture of powdered quartz and powdered magnesium.


2

Mg+Si0

MgO+Si.

a brown powder which burns, when Amorphous heated in the air, to silicon dioxide. It is attacked by hydrofluoric add, but not by other acids.
silicon is
356

SILICON COMPOUNDS.
Si+2
Silicon
is

357
2.

HF
2

SiF4 +2

obtained crystalline by heating sodium


zinc.

fluosilicate,

Na SiF
2

6,

with sodium and


2

Na SiF +4 Na
6

NaF+Si.
zinc,

The

silicon dissolves in the

melted

and separates out

in

crystals as the, zinc cools.

When

the zinc

solidifies it encloses

the silicon.

The

zinc

is

then removed by treating the mass

with hydrochloric acid; and silicon remains. The crystalline form of silicon does not burn in air or oxygen, nor does it dissolve in acids. It dissolves in hot sodium hydroxide solution, giving sodium silicate and hydrogen. The
simplest equation
is,

Si+4

NaOH

Na Si0 +2
4 4

2.

Silicon is made on a large scale, at Niagara, by heating quartz sand with coke in the electric furnace. It is used in making
steel (cf.

488).

Si0 2 +2

Si+2

CO T

of silicon

The general structure Compounds. like of the corresponding is that compounds carbon compounds. Hydrogen silicide, SiH 4 cor389. Silicon
, ;

silicon tetrachloride, responds to marsh gas, CH 4 silicon dioxide, SiCl 4 to carbon tetrachloride, CC1 4
,
;

Si0 2

to
,

carbon dioxide,

C0
3
.

silicic

chloroform,

SiHCl 3

to chloroform,

CHC1

Hydrogen silicide is a colorless gas. It may be obtained, mixed with hydrogen, by treating magnesium
silicide
2

with dilute hydrochloric acid.

Mg Si+4 HC1

SiH4 -l-MgCl2

358

SILICON
ordinarily made,
it

AND BORON.
ignites spontaneously in the

As
air.

SiH4 +2

Si0 2 +2

H O.
2

prepared by heating powdered quartz Magnesium with an excess of magnesium powder.

silicide is

4
If
(cf.

Mg+Si0

>
is

Mg Si+2 MgO.
2

too
388).

little

magnesium

used,

amorphous

silicon results

Silicon tetrachloride

is

a colorless liquid, boiling


silicon
silicic

at 59

C.

It

is

formed from
it,

Water decomposes
chloric acid.

giving

acid

and chlorine. and hydro-

SiCl 4 +4
(Cf.

Si(OH) 4 +4 HC1.
of

the

action

phosphorus
is

trichloride

with

water,

354.)

Silicon tetrafluoride

silicon dioxide is treated

a colorless gas, formed when with hydrofluoric acid. SiF 4 +2

SiO 2 +2
is.

HF
2

H O.
2

Silicon tetrafluoride

is

decomposed by water as the


Si(OH) 4 +2

tetrachloride

SiF4 +4

HF
2

2.

Instead of being set free, however, the hydrofluoric acid unites with some of the silicon tetrafluoride, forming fluosilicic acid,

H SiF
2

6.

The name

"

fluosilicic acid

"

means
(cf.

silicic acid,

H Si0
2

3,

oxygen replaced by fluorine, atoms by six univalent fluorine atoms


its

with

three bivalent

oxygen

365, sulpharsenites,

and sium

268, thiosulphates]
fluosilicate,
salts.

Many fluosilicates
is

are

known; potas-

K SiF
2

6,

one of the few

difficultly soluble

potassium

SILICON DIOXIDE.
390. Silicon Carbide.
Silicon carbide

359
(SiC) or

carborundum

is

among

the three hardest substances

known, the others being boron carbide and the diamond. It is made by heating a mixture of powdered quartz, coke, saw-dust, and common salt in the
electric furnace.
is not attacked by acids nor by solutions of burns only with great difficulty. Because of its hardness, powdered carborundum is used as a polishing and

Carborundum
It

alkalies.

cutting agent.

391. Silicon Dioxide.

Silicon dioxide

is

found as

sand,

may

The pure substance 387). (cf. be prepared by heating silicic acids, H 4 SiO 4 H 2 Si0 3 etc. H 4 SiO 4 Si0 2 +2 2 0. SiO SiO 2 -hH2 O. 2 3
quartz, etc.
,
,

Silicon dioxide

is

thus

silicic

anhydride.

When any form of silicon dioxide is fused with sodium or potassium hydroxide or carbonate, sodium or potassium silicate
results.

NaOH+Si0 Na C0 +SiO
2
2

>

Na Si0 +H 0. Na Si0 +C0


2

2.

Calcium carbonate acts

in the

same way.
is

When
also

silica is
(cf.

fused with the oxide of a metal, a silicate


162).

formed

CaO+Si0 2
Acids do not act upon
acid as in
389).

CaSi0 3
silica

(except hydrofluoric

360

SILICON

AND BORON.

When a soluble silicate is 392. Silicic Acid. treated with hydrochloric acid, a bulky mass, like
gelatine, is precipitated.
orthosilicic acid,
is

This probably consists of

the gelatinous mass dried at the ordinary temperature, it loses water


4

H SiO4.

When

and becomes a non-crystalline powder.

This

is

When the 2 SiO 3 probably ordinary silicic acid, is heated to a powder high temperature it loses water, forming silica, SiO2. The equations are given in 391.
.

Polysilicic

Acids.

Besides the ortho and ordinary forms

of silicic acid, many other forms are possible; these are known as polysilicic acids. They are derived from orthosilicic acid

by the loss of different proportions for them all would be,


a;

of water.

general formula

Si(OH) 4 -2/

H O.
2
2 7.

Thus,

if

x = 2 and y =

1,
4

we

have,
4
2

2H Si0 -H
Among
agate,
all

= H 6 Si
flint,

found in nature are These etc. contain water, and may, therefore, be looked upon as forms
the varieties of amorphous
opal,
silica

chalcedony,

carnclian,

amethyst,

of the polysilicic acids.

The

colors of these substances are

usually due to traces of impurities.

-393. Silicates.
acid.
2

The
is

silicates are salts of silicic

The mineral
4.

chrysolite is
3
2

magnesium
7.

silicate,

Mg Si O These are salts Serpentine of the acids H Si0 and H Si respectively. PotasMg Si0
4 4
6 2 7,

sium, sodium, and calcium

silicates are

derived from

the acid

H Si0
2

3.

GLASS.

361
;

Potassium and sodium silicates are known as " water glass " they are used to make cements and artificial stone. Kaolin is practically pure aluminum silicate, H^^SiO^AO. It fuses at a very high temperature. It Is used for making china and crockery ware, fire-bricks, etc. Clay, which is impure aluminum
silicate,

bricks, etc.

melts lower than kaolin; it is used for making pottery, The red color of baked clay is due to ferric silicate,
.

Fe 2 (Si0 3 ) 3

394. Glass.

Glass

is

a mixture of certain
silicate
is

sili-

cates, generally of

sodium or potassium
silicate.

with
also

calcium or lead
present.

Silicon

dioxide

silicates of calcium, lead, etc., crystallize when they soa glass made from them would break into fragments on The silicates of sodium and potassium, however, not cooling. only do not crystallize themselves, but even prevent the other

The

lidify;

silicates

from

crystallizing.

Ordinary, soft glass, such as is used for window panes and bottles, is essentially a mixture of the silicates of calcium and
sodium.
It is

made by melting

together

silica,

calcium carbonate,
feet high

and sodium

carbonate, in fire-clay pots

about 4

and 4

feet in diameter.

Carbon dioxide
a mixture of the

escapes.
silicates of

Hard
sium.
etc.

glass
is

is

calcium and potas-

used for making chemical apparatus, lamp globes, Crown glass is a variety of it. Jena glass is a hard glass
It

containing boron trioxide.


etc., is

Flint glass, such as is used in making optical instruments, a mixture of potassium and lead silicates.

or " milky " glass is made by adding cryolite (cf. 316), tin oxide, etc., to ordinary glass. " " Granite ironware " or " ware consists of porcelain-lined

Enameled

iron covered with an easily fusible glass, called enamel.

362
Color
is

SILICON

AND BORON.

of other substances.

imparted to glass by the addition of small amounts Thus, a cobalt compound colors glass blue;

a cuprous compound, red; a chromic compound, green. The etching of designs on glass is done with hydrofluoric
acid, as described in

glass the melting pots into hollow cylinders several feet long, and feet in diameter. These are cut open lengthwise, and about

Window

is

made by blowing

318, or with a sand blast. the viscous material from

flattened out in ovens.

Plate glass

is

and rolling it out with heated and polished.

made by pouring melted glass upon iron plates, rollers. The plates are then ground

Bottles, etc., are made by attaching lumps of the viscous glass to hollow tubes, and blowing the glass out in molds.

Pressed glassware is made in molds; in cut glassware the designs are ground or polished by means of emery, carborundum, or sandstone wheels. All articles of glass, to be permanent, must
be annealed. Annealing consists in allowing the hot object to cool regularly, so that its molecules may assume permanent positions with reference to one another. Unannealed glass may
fly

to pieces at the slightest jar.

B.

Boron.

The element boron is 395. Occurrence of Boron. the first member of the aluminum group of elements
(cf.

383)

yet in

its free state it closely

resembles
chiefly

silicon

and carbon.

It

occurs
as borax

in

nature

as boric

add (H 3 BO 3 ) and

(Na2 B 4 O 7 ).

Boric acid is found chiefly in Tuscany, where it issues, mixed with steam, from the earth. Borax is found in Nevada and California in dry borax lakes. Boracite,
occurs at Stassfurt, in Germany.

BORIC ACID.

363

Boron exists in two allotropic 396. Preparation. the forms, amorphous and the crystalline; it is
difficult to

prepare either form in a pure state.


is made by heating boron trioxide, B 2 3 The aluminum reduces the oxide; and the
,

Crystalline boron

with aluminum.
the cooled mass

liberated boron dissolves in the excess of


is

aluminum.

When

treated with hydrochloric acid, the dissolves, leaving crystals of boron.

aluminum

397. Properties.

gravity of 2.6, and

Crystalline boron has a specific resembles the diamond. The


It burns

amorphous form
the
air,

is

brown.

when heated
Nitric

in

giving boron trioxide,


it

2 03.

acid
is

converts

into boric acid.

The

crystalline

form

more
borate.

difficult to ignite

than the amorphous.


sodium hydroxide, giving sodium

Boron

dissolves in melted

When

it

is

boron nitride,

BN.

heated in nitrogen or ammonia it gives This is a white powder which is decomposed

by steam, giving

boric acid
2

and ammonia.

BN+3 H
With
liquid.

B(OH) 3 +NH3
trichloride,

chlorine,

boron forms boron

BC1 3 a
,

colorless

decomposed by water, giving boric acid and 354 and 389). hydrochloric acid (cf.
is

This

BCls+3

B(OH) 3 +3 HC1.

Boric acid is made by adding 398. Boric Acid. concentrated hydrochloric or nitric acid to a hot solution of borax. It is a white, crystalline solid.

aqueous solution has a faintly acid reaction with litmus, but colors turmeric paper brown, just as
Its

364

SILICON

AND BORON.
Boric
acid
is
is

sodium hydroxide does.

in

some

respects like aluminum hydroxide, which or a base, according to circumstances.


Boric acid
is volatile

an acid

with steam, as was indicated in

395.

Its solution in ethyl alcohol

When

boric acid

hydride,

3.

is heated it This redissolves readily in water, giving the acid.

burns with a bright green flame. loses water, giving finally the an-

The ordinary borates are derived 399. Borax. but from tetraboric not from the ortho acid, 3 BO 3 the ortho acid just is related to B This 4 2 7 acid,

as the polysilicic acids are to orthosilicic acid


392).

(cf.

H BO -5 H O
3 3 2

-H

7.

Borax
into the

is sodium tetraborate, Na2 B 4 7 market as crystals which are either


.

It

comes

10

H O or NaeB
2

7 .5

H O.
2

When heated, borax loses its crystal-water and swells to a porous mass; on stronger heating, this melts to a clear glass. Molten borax dissolves the oxides of metals, and with some of
them
of

gives characteristic colors; hence, its use in the laboratory " borax bead," and in the arts to clean the surfaces to form the

metals before soldering and welding, and before coating


(cf.

metals with enamel

394).

We may
i. e.,

look upon the borax molecule as 2 as sodium metaborate plus boron trioxide.
162, 357,

NaB0 +B
2

3,

The

oxides of

metals react with the boron trioxide to give other metaborates


(cf.

and

391).
2 3
2

CoO+B Fe +3 B
2

>
3

Co(B0 2 ) 2 > 2 Fe(B0 2) 3


.

EXERCISES.
Borax
is

365

used, also, to prevent the decomposition of organic


of

substances, in medicine, in the manufacture soaps, and to increase the gloss of starch.

hard-water

400. Exercises.
1.

Name some

of the scouring mixtures

which consist

es-

sentially of silica.
2. Suggest a possible reason for the fact that silicon dioxide a hard, infusible solid, while the corresponding oxide of carbon

is
is

gaseous.

3. Name some polishing, or abrasive, agents besides silica and carborundum. How are diamonds polished? 4. From some of the facts named in this chapter suggest a way in which carbon dioxide might be liberated from calcium

carbonate in the earth's crust.


5.

What

class of substances

must be present

in

underground
substance

waters so that silica


is

may

be held in solution?

What

needed to hold calcium carbonate in solution?


6.

From what
5

polysilicic acid

would a

silicate of

the formula

CaSi 2

be derived?

Show

the relation of this acid to normal

silicic acid.

7. What are the proportions, by volume, of factors and products in the equation representing the combustion of hydrogen
silicide (cf.

389)?

CHAPTER XXIX.
METALS.
In our previous Metals and Non-Metals. non-metallic elements. studied work we have chiefly There is, however, no sharp distinction between metals and non-metals, but rather a gradual change from one class to the other (cf. 378). But just as oxygen, chlorine, and sulphur have a distinct character, which no one would mistake for that of a metal, so
40.1.

there are certain elements having a typical metallic


nature.

Metals are usually opaque, and their polished surfaces are good reflectors of light; hence the metallic luster. They are good conductors of heat and With oxygen and hydrogen the metals electricity. form bases, and by replacing the hydrogen of acids, i. e., ionic hydrogen, they form salts.
Some elements, e. g., antimony, are both acid-forming and base-forming; they are often called metalloids. Besides the general properties already given, metals possess
other properties in varying degrees. Thus, some metals, e. g., sodium and had, are soft; while others, e. g., chromium and

manganese, are hard. Sodium and lithium are light enough to float on water; while gold is 19.3, and platinum 21.5 times as Metals having a specific gravity less than 5 heavy as water. " " " " are called light metals; those above 5 are called heavy
metals.

OCCURRENCE OF METALS.
402. Occurrence

367

and Extraction of Metals. The solid elements and compounds found in nature The minerals and mixtures are called minerals. of minerals from which metals are obtained are called Some metals, e. g., gold and copper, occur ores.
free,

that is, uncombined with other elements; but most metals are found as oxides or sulphides.

carbonates, sulphates, phosphates, etc.

Some occur

as

hydroxides,

chlorides,

If metals occur free, they may be separated by mechanical means from minerals mixed with them. An illustration is the crushing of an ore in a stamp-

and the washing away of the lighter materials. Copper and gold are extracted in this way, although chemical methods are employed with inferior ores of
mill,

these metals.

The most common method

of extracting metals

is

to reduce the oxide with carbon (charcoal or coke). This is the case with iron. If the ores used are not oxides, they are usually converted into oxides by

"

"

roasting carbonates

(cf.

may

Sulphides, hydroxides, thus be changed into oxides.


of reducing

252).

and

Another method
of hydrogen.

an oxide
is

is

to heat

it

in

a stream

The oxygen and hydrogen


is left.

unite and escape as

steam, while the metal

This

a good laboratory method;

but

it is

too expensive for commercial use.

sodium.

Chlorides are sometimes reduced by heating them with Aluminum was formerly obtained in this way from its

chloride.

368

METALS.
e.
g.,

Several of the metals, and calcium, are obtained


tric

aluminum, sodium,
of the elec-

by the action

current

upon some

of their

compounds.

When two or more melted metals 403. Alloys. form a uniform mixture (cf. 78), the mixture is If mercury is one of the metals, called an alloy. the alloy is called an amalgam. Alloys resemble solutions in many ways. Thus, melted tin and lead, like alcohol and water, mix in any proportion, but zinc and lead, like ether and water, only to a If a metal is mixed with limited extent (cf. 82). even a small per cent of another, it undergoes a
marked change
ture,

in properties;

the melting temperafor

the

malleability,

and the conductivity


;

heat and electricity are lowered (cf. the 374) hardness is increased (cf. 367, 458, 464, and 470). Copper containing 0.8% of arsenic has only 30%
of the electric conductivity of

pure copper.

- - The metals 404. Classification of the Metals. may be classified and studied according to several
systems is that of Qualitative Analysis," a branch of Chemistry in which we identify the common metals and acid radicals present in a mixture.
systems.

One

of these

"

The
(1)

Qualitative scheme
(cf.

is

sulphides

255)

These

may

based upon the properties of the be classified as,


(see

soluble, including sulphides of Groups I and II

below) ;

CLASSIFICATION OF THE METALS.


(2)
(3)
:

369

moderately insoluble sulphides of Groups III and IV; The very insoluble sulphides of Groups V and VI.
:

Qualitative grouping
Group
I.

is

as follows

370
5.

METALS.
Aluminum.
is

Aluminum

is

trivalent,

and forms a hy-

droxide that

both an acid and a base.

The hydroxides of these and Nickel. 6. Iron, Cobalt, The compounds are of two series: metals are feeble bases. " " and " ic," in which the metal is bivalent and trivalent, ous
respectively.
7.

acid properties of the oxides increase with the increasing per cent of oxygen. 2 07 is the anhydride of

oxide

Manganese. MnO. The


acid.

Manganous

salts

are

derived

from the

Mn

permanganic
8.

The oxide Cr 2 03 is basic, giving chromic but CrOs is the anhydride of chromic acid. These belong to the carbon family. The 9. Tin and Lead. oxides and hydroxides in which the valence of the metal is 2
Chromium.
salts;

Those in which it is 4 and plumbates. 10. Platinum. The platinum and palladium divisions of periodic group VIII, together with gold, silver, and mercury, are called noble metals. The others are base metals. The noble metals are chemically inactive, and their oxides and salts
are both
acids.

weak bases and weak

are stronger acids, giving stannates

are decomposed

by

heat.

and Appendix x) we have an arrangement in which the metals coming first displace those that follow, from solutions of their salts. The series represents much more than this. Thus, the metals coming first are active, and form
series of

405. Electromotive Series. 180 the metals (cf.

In the electromotive

Their hydroxides are strong bases. end of the series (" noble " metals) are inactive, and form unstable oxides. Since their oxides are unstable, metals like gold and platinum
stable oxides.

The metals

at the

occur free, while potassium, etc., do not.

The

oxides

COMPOUNDS OF THE METALS.

371

from gold to mercury, inclusive, are decomposed by heat; those from arsenic to manganese are reduced by hydrogen and carbon; while those above manganese are neither decomposed by heat nor readily reduced. Naturally, the metals coming first in the
series

were the

last to

be discovered and prepared

by man.

406.

Compounds

of

the

Metals.

The

comhy*

pounds

of the metals are classified as oxides,

Oxides and hydroxides of droxides, and salts. metals are bases in the presence of water. Salts

may

be normal,

acid, or basic

(cf.

163 to 165).

Oxides of metals are nearly all insoluble. Some, however, Oxides may be react with water to give soluble hydroxides. made by the oxidation of metals (cf. 24), and by the decomposition of hydroxides, carbonates, nitrates, etc., by heat. Hydroxides of the alkali metals and of the alkali-earth

metals, except magnesium, are soluble. All other hydroxides are insoluble. Hydroxides are made by the union of oxides and water
(cf.

161), or

Salts are
(1) (2) (3) (4)
(cf.

by double decomposition made by,

(cf.

459 and 476).

Union

of metals and non-metals (cf. Reaction between metals and acids

118)
(cf
.

47)

Neutralization.

Reaction between an acid and the


126);

salt of

a volatile acid a volatile base

(5)
(cf.

Reaction between a base and the


203);

salt of

(6)

Double decomposition between

salts.

372
The occurrence
of

METALS.
sulphides, their preparation, and their 253 to 255, and in 404 (q. t>.).

properties are given in

Chlorides, bromides, and iodides are

made by

the general

many cases the anhydrous submaking stance can be prepared only in the absence of water, since evaporation of the aqueous solution causes hydrolysis (cf. 441).
methods
of
salts.

In

Practically

all

halides are soluble except those of lead, silver,

and mercury
Nitrates
hydrolyzed.

(ous). are soluble, although

some,

e. g.,

Bi(N0 3 )3,
.

are

All are

decomposed by heat

(cf.

230)

Nitrites are also soluble.

They

are decomposed

by strong

234). acids, giving nitrogen oxides (cf. The normal sul259). Sulphites are normal or acid (cf. phites of the alkali metals are soluble; other normal sulphites

are insoluble. are

Most

acid sulphites are soluble.

All sulphites

decomposed by

strong acids.

Sulphates are formed by the general methods; some by the


oxidation of sulphides, e. g., CuS+2 CuSOi. All sul2 phates are soluble except those of lead, barium, and strontium.

Carbonates are
Since carbonic acid

insoluble,
is

weak,

except those of the alkali metals. its salts with weak bases are com-

pletely hydrolyzed in the presence of water.

Fe 2 (C0 3 ) 3 +6
All
dioxide.

Fe(OH) 3 j

+3 H2C0

carbonates

are

All are readily

the alkali metals, of


metals.
ar V
(cf.

decomposed by acids, giving carbon decomposed by heat, except those of barium, and of strontium.
insoluble, except those of the alkali

Phosphates (normal) are

The common
357).

soluble phosphates are primary or second-

Those produced by precipitation are generally

tertiary (normal) orthophosphates. Silicates of the alkali metals are soluble; others, insoluble. All are decomposed by acids, giving silicic acid. In the meta-

phosphate or borax bead


"
silica

silicates

are insoluble,

and form a

skeleton."

EXERCISES.
407. Exercises.
1. Classify

373

and

"

2.

heavy Enumerate the

"

the metals of the Qualitative groups into metals,


alloys described in this book,

"
light

"

and give the

uses of each.
3. If you had a solution containing of all the metals of the Qualitative grouping,

a mixture of the nitrates

how

could you

separate the metals of Div. I, Group V, from all the others? How could you separate barium, lead, and strontium from all the others? How separate Groups I and II from all the others? of 4. What difference would there be between the action

sodium hydroxide upon aluminum hydroxide and

its

action

upon magnesium hydroxide? Why? 5. Why would the metals at the bottom
series

of the electromotive

When primitive naturally be discovered first? abandoned stone as the material of his tools, weapons,

man
etc.,

what metal might he be expected to find that possessed the necessary properties, and was sufficiently abundant for his use? at once? What metals made up Why would he not use iron " " " bronze "? What was the Bronze Age ?

CHAPTER XXX.
THE ALKALI METALS.
-- The metals, like the 408. General Properties. non-metals, are generally studied in groups or natural
families based

Alkali group and the radical

similarity of properties. of the five metals named consists

upon

The
below

ammonium,

NH^

the compounds of

which resemble those of sodium and potassium " " alkali metals 210). These metals are called (cf. of the members the two most because important group are contained in the alkalies, i. e., in sodium

and potassium hydroxides.

ELEMENT.

SODIUM.

375

of the oxide and the hydroxide; if carbon dioxide is present, these pass into the corresponding carbonates. The alkali metals burn when heated in air, and de-

compose water at ordinary temperatures; therefore none of them is found free in nature. The salts of
these metals are practically
all

soluble in water.

The

properties of the alkali metals change in the order of the


e. g.,

atomic weights,

melting-point. character increase from lithium to coesium.


electro-positive element

The chemical

the higher the atomic weight the lower the activity and the electro-positive

Cesium

is

the most

known.

409. Lithium.

Lithium

is

widely distributed in

nature, but no mineral known contains a large proportion of it. It is found in minute quantities in most

mineral waters, in many plants, and in the blood. Lithium is the lightest of the metals. Its salts color
the Bunsen flame crimson.

Sodium occurs widely distributed 410. Sodium. and in large quantities, especially as sodium chloride, NaCl. This exists as rock-salt and sea-salt, and in

many many

mineral springs. Sodium silicate is found in Large rocks; the nitrate is Chili saltpeter.

deposits of the sulphate and carbonate exist. The ashes of plants growing in or near the sea contain sodium carbonate, and were formerly the source of

many sodium compounds.

376
Sodium
is

THE ALKALI METALS.


prepared by the electrolysis of melted sodium hyThis is Castner's process. The resistance of
the hydroxide generates the heat that keeps it melted, after the operation has

droxide (Fig. 81).

begun. droxide
is

The
is

vessel containing the hy-

of iron,

and the anode (BB)


iron

either a

cylindrical

or nickel

vessel, or a number of pieces of gas carbon. The cathode (^4.), extending

up

carbon.

into the hydroxide, is of iron or When the current passes,


of

globules

sodium

collect

upon the

cathode, and rise to the top at Na. They accumulate in the collecting
cylinder (Na, H) which floats on the melted hydroxide, just over the cathode.

The lower part

of

the

collecting

cylinder

consists

of

wire

gauze (shown by dots), which prevents the globules of sodium

from going to either oxygen at the anode:


4

side.

The anion (OH)

gives water

and

OH+4(+)

2H 0+0
2

T.

Electrolysis of some of the water gives hydrogen at the cathode and more oxygen at the anode. The hydrogen accumulates with the sodium in the collecting cylinder (Na, H}, and protects the sodium from the air (cf. 54). The melted

sodium

is

removed by means

of ladles, while the hydrogen

escapes under the cover (L). The oxygen (0) is conducted away with great care, to prevent its coming in contact with the other

products.

Sodium is a white 411. Properties of Sodium. so soft at metal, ordinary temperatures that it can

PROPERTIES OF SODIUM.

377

be molded between the fingers, or pressed into wire. At 20 C. it is quite hard. It has the characteristic
properties of the metals, including conductance for

heat and electricity (cf. molecule is monatomic (cf.


sium.

74, 401,

and
is

408).

The

142)

so

that of potas-

Sodium burns in air or oxygen with a bright, yellow flame. The same characteristic color is imparted to a non-luminous flame by any sodium compound, and serves as a test for the element.
Sodium burns
sulphur vapor.
It acts

118) and in energetically in chlorine (cf. upon alcohol much as upon water, form-

ing sodium ethylate and hydrogen

2
It

C2H 5 OH+2 Na

(cf.

220)

carbons, and

does not react with ether, nor with the liquid hydrois usually kept under ligroin or kerosene (cf. 525).

When
An

exposed to ordinary air


alloy of
is

it

is

soon converted into the

carbonate.

sodium and mercury, called sodium amalgam an important reducing agent; it is diluted sodium. When sodium is burned in air or oxygen, the product is a mixture of the monoxide (Na 2 0) and the peroxide (Na20 2). The 339), peroxide is the sodium salt of hydrogen peroxide (cf. It is a powerful oxidizing and bleaching agent.
(cf.

403),

(1)

Na
2

2 2

+2 HOH
2

(2)

The monoxide is made by beating sodium nitrate or hydroxide with sodium, in the absence of air.
2 2

NaNO +10 Na NaOH+2 Na


3

- "
t

2
2

NaOH+H
(nascent;

2.

H 0+0
2

cf.

340).

>

Na 0+N 2 Na 0+H 2 T
2 2

T
.

378
412.

THE ALKALI METALS.

Sodium hydroxide, or Sodium Hydroxide. caustic soda, is formed when sodium or its oxides react with water. The commercial methods of preparing it are :

Boiling a solution of sodium carbonate with slaked lime (calcium hydroxide).


(1)

Na 2C0 +Ca(OH)s
3

2NaOH+CaC0

j.

FIG.

82.

The
rated.

calcium

carbonate
is

is

precipitated.
off

The

sodium hydroxide solution

drawn

and evapo-

(2) Electrolysis of aqueous sodium chloride (Castner's process).

2NaCl

(2Na)+CU. (2Na)+2HOH 2NaOH+H

T.

SOAP.

379

The
(3)

last

two products

collect at the cathode.

Electrolysis of fused

sodium chloride (Acker

process).

The apparatus

is

shown

in Fig. 82.

The carbon anodes (A, A, A) dip into fused sodium chloride. This floats upon melted lead (solid black of figure), which is in contact with the cast-iron box (), and forms the cathode. The sodium forms an alloy with the lead, while the chlorine is
carried away at Cl, to be converted into bleaching powder. The sodium-lead alloy passes into compartment E, in which a jet At the same time the of steam (S) forces the alloy over into

steam reacts with the alloy, forming lead, sodium hydroxide and hydrogen. The hydrogen burns. The melted lead collects under the sodium hydroxide, and is returned through the pipe Pb to compartment D. The sodium hydroxide is transferred " to metal drums," which form the commercial packages.

Sodium hydroxide

very soluble in water.

203). agent (cf. absorb carbon dioxide readily. Sodium hydroxide is one of the strongest and most useful bases. Enormous quantities of it are used in " softening " water,
in

a white, deliquescent solid, solid is used as a drying Both the solid and its solution
is

The

making
525).

soap,

and

in various chemical industries

(cf.

When fats are boiled with alkalies, 413. Soap. they are saponified, i. e., converted into soap. Thus
stearin/ which is glyceryl stearate (cf. 540), caustic soda give sodium stearate and glycerine.

"

and

The
is

sodium
soap.

salt of

the organic acid (here, stearic acid)

380

THE ALKALI METALS.

C3H

/O-CO-C H
17
7 5

35

HONa

0-CO-Ci H
7

35 35

+ HONa
HONa
sodium hydroxide

\0-CO-Ci H
glyceryl stearate

/OH
CaHs

OH+3

NaO. CO. C 17 H 35
sodium
stearate

\OH
glycerine

The sodium

stearate formed

is

(soap) " " salted out of solution

by

adding sodium chloride.


is dissolved in water it is partly hydrolyzed (cf. sodium hydroxide and the organic acid; the sodium hydroxide is the cleansing agent. When soap is put into hard water, an insoluble scum is formed; this is the calcium salt of

When

soap

184) into

the organic acid.

Sodium Carbonate. Sodium carbonate, or one of the most soda, important chemicals manufactured. The principal methods of making it are the Solvay, or Ammonia, Process and the Le Blanc Process. The second of these is the more interesting historically, because it was devised by Le Blanc for the French government during the Revolution, when the supply was cut off; but the ammonia process is
414.
is

so

used with

much cheaper that fully three-fourths of the soda is now made in this way. Both processes begin common salt.
essentially in treating

chloride

The Solvay Process consists with ammonium hydrogen

sodium

carbonate,
4

NH HC0
4

3.

NaCl+NH HC0
4

NH Cl+NaHC0

SODIUM CARBONATE.

381

This reaction takes place because sodium hydrogen carbonate (sodium bicarbonate) is not very soluble in water and is, therefore,
is

when ammonium hydrogen carbonate salt solution. The solution of ammonium hydrogen carbonate is formed by passing carbon dioxide under pressure into a saturated solution of ammonia (NH4 OH)
readily precipitated

added to concentrated

NH OH+H C0
4
2

NH HC0 +H 0.
4
3

Gentle heating converts the bicarbonate into carbonate.


2

NaHC0

Na C0 3 +H 2CH-C0 2
2

all

The carbon dioxide thus set free is used again; and nearly the ammonia is recovered by heating the brine, from which,
(cf.

the bicarbonate has crystallized, with slaked lime

203).

The Le Blanc Process


tions:
(1)

consists of

essentially three opera-

The conversion

of

common

salt into

sodium sulphate

(cf.

126);

2
(2)

NaCl+H S0
2

Na S0 4 +2
2

HC1.

The reduction

of

sodium sulphate to sodium sulphide;

Na 2S04 +4 C
(3)

Na S+4 CO.
2

The conversion

of

sodium sulphide into the carbonate;

NaaS+CaCOs
The

Na C0 3 +CaS.
2

second and third operations take place together, sodium sulphate being mixed with limestone and coal-dust and the

mixture heated.

The sodium carbonate cannot readily be separated from calcium sulphide because both are soluble. If limestone is present in excess, however, some of it is dissociated
into quicklime (CaO) and carbon dioxide; the quicklime and the calcium sulphide form an insoluble compound.

382

THE ALKALI METALS.

Soda comes into the market as calcined soda, or soda-ash, containing no crystal water, and as crystalSoda is used lized soda or sal sodae, Na^COs. 10 H 2 0. in great quantities in the manufacture of glass 394) and of sodium hydroxide ( 412), and to (cf.
soften water.

Sodium bicarbonate Sodium Bicarbonate. normal salt with carbonic is prepared by treating the The equation for its decomposiacid (cf. 284).
415.

by heat is given in 414. It is used in large amounts for baking powders, effervescing mixtures, " soda-water," and medicine.
tion

The common phosdisodium hydrogen phosphate, phate of sodium Na2 HP0 4 12 2 O; it is formed by adding sodium carbonate to phosphoric acid until the solution is
416.

Sodium Phosphate.
is
.

slightly alkaline.
Phosphoric acid
are usually normal,
is tribasic
e. g.,
(cf.

355)

and
,

its insoluble salts


;

Li 3 P0 4j
is

Ca 3 (P0 4 ) 2 Ag3 P0 4

but

its

normal sodium
that
it

so readily hydrolyzed absorbs carbonic acid from the air.


salt

(Na 3 P0 4 )

(cf.

357)

Na P0 4 +H 2 C0
3

Na HP0 +Na C03


2 4 2

mon

chloride, or comIt makes up salt, occurs widely distributed. about of sea-water, and is found in large deposits

417.

Sodium

Chloride.

Sodium

3%

in Galicia (Austria),

States, etc.

In some places salt

Germany, England, the United is mined as rock-salt,

OTHER SODIUM SALTS.

383

while in others the mixture of salt and earth is treated with water, the resulting brine being pumped to the

and then evaporated. In modern plants the concentrated and the salt continuously sepa" rated in a vacuum " boiler.
surface

brine

is

Sodium
which

decrepitate (cf.

chloride crystallizes in colorless, transparent cubes, 88) when heated. It is only a little more
(cf.

soluble in hot than in cold water


Salt
is

80).

necessary to the life of man and other animals, the hydrochloric acid of the gastric juice being derived from it 125). It is used in enormous quantities, not only as food, (cf.

but as the starting material in the preparation of most compounds of sodium and of chlorine.

418.

Sodium
it

Nitrate.
(cf.

Chili saltpeter
cent,

231).

Sodium nitrate occurs as It is somewhat deliques-

hence

gunpowder. which is not


(cf.

cannot be used for the better grades of It is converted into potassium nitrate,

223). 358).
(cf.

deliquescent, and into nitric acid Sodium nitrate is also used as a fertilizer

(cf.

The crude
323).

salt is

an important source of

iodine

419. Other

Sodium

Salts.
salt

made
(cf.

(in

two

stages) from

Sodium sulphate is and sulphuric acid


is first

126).

The

acid salt

(NaHSO 4 )
is

formed.
salt

The normal salt, i. e. its hydrate, and magnesium sulphate solutions.


2

formed from

NaCl+MgS0

Na S0 4 +MgCk
2

384

THE ALKALI METALS.


is

" Glauber's Salt "


is

the decahydrate,

Na^.

10

H 0.
2

It

effloresces completely in

dry

air.

The

principal use of

sodium

sulphate

Sodium sulphide, Na 2S,


method
(

as a substitute for soda in glass-making. " " is prepared by the neutralization


;

254)

also

by the

large, deliquescent crystals.

reduction of the sulphate. It forms In solution it is hydrolyzed, giving

the hydrosulphide and the hydroxide. behave in the same way.


.

Other soluble sulphides

Na 2S+HOH
Sodium sulphide

NaSH+NaOH.

Na S Na S
2
2, 2

3,

etc.

unites with sulphur, forming poly sulphides, Potassium and ammonium sulphides do the

same

(cf.

427).
.

Sodium thiosulphate (Na 2S 2 3 5 H 20) is described in 268; sodium tetraborate (Na 2B 4 7 10 H 2 0), or borax, in 399. Sodium cyanide, NaCN, is a soluble, white solid, used in
.

to extract gold from poor ores (cf. 468). purpose by the reaction between ammonia gas, sodium, and carbon. It resembles potassium cyanide (q. v.}.
the
It

"

"

cyanide process
for this

is

made

a constituent of potash feldspar and mica many rocks, 472), and by their disintegration becomes a (cf. part of the soil. Plants require potassium salts for their growth (cf. 358), and potassium carbonate in is found (potash) plant ashes. The residues left
420. Potassium.
is

Potassium

such

as

after sugar is extracted from beets ( 543) the argols of wine casks (cf. 538), and suint, a substance ob,

tained in the washing of sheep's wool, all contain potassium salts. When these (and other) potassium
salts of organic acids are

burned, potash

is left.

POTASSIUM HYDROXIDE.
The most important
source of potassium

385
compounds at

present are the deposits at Stassfurt, near Magdeburg, Germany. Here, on top of a layer of salt about 4,000 feet in thickness, are layers about 90 feet thick, which contain potassium salts, either " " double salts of potassium with magnesium salts, alone, or as

calcium
carnallite

salts,

etc.

Some
,

of these salts are:


2

sylvite
,

(KC1,

MgCl 2

H 0),
,

(KC1),
,

and polyhalite (K 2S0 4 very exact methods of solution and recrystallization the potassium salts are separated from the others.
6
2
,
,

H 0),

(MgS04 MgCl 2 K 2S0 4 MgS04 2 CaS04 2 H 20). By


kaintie
,

Potassium

is

made by

the electrolysis of either

potassium chloride or the hydroxide (cf. 410). It is a soft metal, like sodium, but has a slightly bluish luster. Like sodium, it must be kept under kerosene
or ligroin.

When

exposed to the

burned,

it

gives the oxide

Na^O, and is (cf. 411): Potassium decomposes water energetiIt is not used to any great extent, cally (cf. 74). since sodium, which is much cheaper, can be used
similar to
instead.

air, and when The oxide, K2 O, is made by similar methods

KO
2

4.

The vapors of potassium and luminous flame violet.


421. Potassium Hydroxide. ide, or caustic potash, is made

its salts color the

non-

Potassium hydrox-

potassium

chloride.

by the electrolysis of The method resembles that for


(cf.

the preparation of caustic soda

412).

It is also

made from potassium carbonate by treatment with


"

milk of lime/

i.

e.,

calcium hydroxide.
2

K C0
2

+Ca(OH) 2

KOH+CaC0

386

THE ALKALI METALS.

Potassium hydroxide is a white, deliquescent solid which unites readily with the water and carbon dioxide of the air. It is used as a drying agent. It is a powerful base, saponifying fats as caustic soda does. Potassium salts of stearic, etc., acids " soft soap." 413) form (cf.

Potassium carbon422. Potassium Carbonate. ate is made by the Le Blanc process from potassium chloride (cf. 414). The crude substance is obtained

when potassium salts posed, as by burning


present in wood-ashes.

of organic acids are


(cf.

decom-

420).

It

is,

therefore,

The anhydrous substance is a powerful dehydrating agent. Potash is used to make the hydroxide and hard

glass.

In chemical analysis, a solid insoluble in acids is converted into soluble substances by fusing it with a mixture of potassium and sodium carbonates. The mixture has a lower melting point

than either carbonate alone. Only one of the carbonates need be


given in the equation.

Barium
2 3

sulphate reacts thus:

BaS0 4 +K C0
If the

BaC0
is

+K S0
2

4.

mixture obtained by fusion

heated with water, the

S04

dissolved (as The residue, 2 S0 4 ), and may be tested for. insoluble in water, contains the Ba (as BaC0 3 ). Dilute nitric
is

++

acid converts
insoluble salt
radical
is

it
is

into Ba,

i. e.,

Ba(N0

3) 2.

When,

therefore,

an

fused with the two alkali carbonates, the acid in the part soluble in water, while the metal is in the
if

insoluble part, either as carbonate, or as oxide or free metal,

the carbonate

is

unstable.

POTASSIUM BROMIDE.

387

results

Potassium chlorate 423. Potassium Chlorate. when chlorine is passed into a hot, concen-

trated solution of potassium hydroxide until the solution is saturated (cf. 331).
6

KOH+3

C1 2

KCl+KClOa+3 H 20.
"

A cheaper way is to pass the chlorine into hot


calcium chlorate, Ca(C10 3 ) 2
,

milk of lime ";

This with potassium chloride gives potassium chlorate and calcium chloride.
is

formed.

Ca(C10 3 ) 2 +2 KC1
Potassium chlorate, being
the other substances,
solution.

KC10 3 1 +CaCl 2

much

less soluble in cold


out,

water than

crystallizes

leaving the others in

Like the nitrate, potassium chlorate is valuable chiefly as an oxidizing agent. It is used in preparing
oxygen, explosive mixtures,
e.
g.,

matches, and fireworks.


"
"

It is sold

smokeless powder, by druggists as

potash

for sore throats.

424. Potassium Bromide (KBr) and Potassium Potassium bromide and potassium Iodide (KI). iodide may be prepared by the action of bromine and
iodine,

The equations
of chlorine
6
6

respectively, upon potassium hydroxide. are analogous to the one for the action

upon

caustic potash.
5 5

KOH+6 Br KOH+6 I

KBr+KBr0 +3 H O. KI+KI0 +3 H O.
3 2 3

By evaporating the solution containing bromide and bromate, or iodide and iodate, to dryness, and then heating the residue

388
sufficiently,

THE ALKALI METALS.


the iodate just

as

we can decompose the bromate and we can the chlorate (cf. 19).
2 2

KBr0 KI03

2
>

KBr+3 KI+3 O

2.

2.

Potassium bromide and iodide are made,

also,

by

treating

the bromide and the iodide of iron with potassium carbonate.

Fe 3Br 8 +4 K 2 C0 3 Fe 3I 8 +4 K2 C0 3

Fe3 4 +8 KBr+4 C0 2 Fe 3 4 +8 KI+4 C0 2


.

The iron compounds are formed by adding bromine and iodine,


respectively, to moist iron turnings.

425. Potassium Sulphates.

When potassium chloride, nitrate, acetate, etc., are treated with concentrated sulphuric acid, the acid sulphate, or bisulphate,
first, and usual, product, as is the case with sodium 126 and 224). The acid sulphate is also formed (cf. from the sulphate and concentrated sulphuric acid (cf. 164 and 267). It forms large crystals which melt readily, and give
4,

KHS0
salts

is

the

off

water, leaving the pyrosulphate

(cf.

260).

Normal potassium sulphate (K 2 S0 4 ) is made from the acid sulphate and the chloride, etc., at red heat (cf. 126); also by
acid.

neutralizing the hydroxide or carbonate with dilute sulphuric It crystallizes from water without water of hydration,

and, except for decrepitation, is stable is found in the Stassfurt deposits (cf.
fertilizer,

when
420).

heated.
It is

The

salt

used as a

and to prepare potassium carbonate by the Le Blanc

process.

426. Other Potassium Salts.


Potassium
nitrate

has been described in

230 to 232.

It

is

made by

the double decomposition of hot, saturated solutions

AMMONIUM

SALTS.

389

it

of potassium chloride and sodium nitrate. When it is heated melts and loses one third of its oxygen, giving the nitrite

KN0

2,

(qf.

234).

This

is

soluble, white, crystalline solid.


is

Potassium cyanide (KCN)


very soluble in water.
hydrolysis.

The
air,

solution

Exposed to

a white, deliquescent solid, is very alkaline, owing to the cyanide is converted into car-

It is very poisonous. bonate and prussic acid (cf. It 290). is used to prepare electroplating solutions (cf. 464), to extract 419 and 468), and as a reagent. Potasgold from its ores (cf.

sium cyanide
rocyanide
(cf.

is

made by heating a mixture of potassium fer496) with potassium carbonate.


4
2]

(1)
(2) (3)

K4Fe(CN) 6

KCN+[Fe(CN) J.
2
2

K C03+[Fe(CN)
2

KCN+(FeC0

3 ).

(FeC0

3)

FeO+C0

t.

Potassium thiocyanate (KSCN)


solid,

is

a soluble, white crystalline


salts.
4
6)

used in the laboratory to detect ferric


tartrate
4

Potassium hydrogen
potassium
tartar
bitartrate,

(KHC H

is

also

called

"
(cf.

253 times

its

cream of potassium acid tartrate, and It is a white, crystalline solid, requiring 280). weight of water, at 10 C., to dissolve it. The
is

"

corresponding sodium salt

very soluble.

427.

Ammonium

Salts.

- - The formation
of

of

monium salts by ammonia water is

the neutralization described in


210.
it

acids

amby

The

radical

NH

has not been isolated, because


hydrogen.

breaks up into
salts are

ammonia and

Most ammonium

white, soluble solids, which, except for their instability, resemble the corresponding potassium com-

pounds.

Ammonium amalgam
bling sodium

is

a bulky, metallic substance resem411).


It
is

amalgam

(cf.

formed when sodium

390
amalgam
chloride.

THE ALKALI METALS,


reacts with a

concentrated solutfon of

ammonium

Na,

Hg+NH Cl
4

NH

4,

Hg+NaCl.

Ammonium amalgam
and mercury.

breaks up into ammonia, hydrogen,

Ammonium chloride is used in soldering, in making galvanized


iron
(cf.

448),

and

in the preparation of

" " for sal ammoniac batteries, as well as ammonia and as a reagent in the laboratory.

Ammonium Ammonium
(cf.

sulphate,
nitrate,

(NH4 2S04
)

NH N0
4

3,

is

is an important fertilizer. a white, deliquescent solid


(cf.
6,

85).

It

is

used in preparing nitrous oxide


tartrate,

238).
is

Ammonium hydrogen

NH HC H
4

difficultly

soluble, like the corresponding

potassium
)2

salt.
4.

Ammonium phosphate is (NH4 HP0


ing sodium
salt, it is

Like the correspond4

used as a source of

P0

in the laboratory.

Ammonium

oxalate,

(NH4 2C
)

4,

is

a source of oxalate ions,

4.

Ammonium
ions of
its

carbonate,

(NH4 ) 2 C03

is

used for the carbonate

solution.

The commercial

salt is

ammonium

sulphate with calcium carbonate. carbonate sublimes (cf. 211).

made by heating The ammonium


4.

(NH S0 +CaC0
4) 2 4

(NH4 C0 3 T +CaS0
)2

The product
of the

is

not pure

(NH4 ) C0 3
2 2

but contains
4.

NH HC0
4

and ammonium carbamate,


impure
pure
salt as

NH COONH

When

the solution

salt is treated with carbon dioxide, it gives the a precipitate. Ammonium carbonate breaks up readily into ammonia, carbon dioxide, and water. For this reason it is used in some baking powders. As " solid ammonia " it
is

used for smelling salts and as a water softener.

Ammonium
It is a

sulphide,

(NH 4

) 2 S,

is

made
(S) in

as stated in

254.

common source of sulphide ions


is

the laboratory.

The

substance

readily dissociated

(NH4

)2

S;=!2NH +H S.
3 2

EXERCISES.
The hydrogen
liberated.

391
air,

sulphide

is

oxidized

by the

and sulphur

is

This unites with the unchanged

ammonium

sulphide
,

to give yellow
etc.

ammonium

sulphide,

The same substance

is

whiqh is (NH4 ) 2 S, (NH4 ) 2S 2 " " formed from colorless ammonium

sulphide and sulphur.

Ammonium

salts

are

used

so

generally

in

the

laboratory because they are soluble, and, further, because they can be removed at any time from a mixture, owing to the ease with which they are dissociated

into volatile materials.


salts is that

The

test for

ammonium

they

all

react with lime, giving ammonia.

428. Exercises.
1. If

the molecule of sodium


liter of its

is

monatomic

(cf.

411),

how

does the weight of a


liter

vapor compare with that of a of oxygen under the same conditions? Answer the same

question for potassium.


2.

What

products would be formed at each electrode in the

electrolysis of

ammonium chloride? Of ammonium nitrate? would you prepare sodium chlorate, ammonium hydrogen carbonate, sodium potassium tartrate, potassium silicate,
3.

How

potassium oxalate, ammonium mono-hydrogen phosphate? 4. Write the equations showing the preparation of potassium carbonate by the Le Blanc process. 419 are soluble. 5. All four substances in the equation of

Under what conditions can the 6. Which of the following


caustic potash:

reaction take place?

gases would

you dry with

solid

ammonia^

chlorine,

hydrogen sulphide, carbon

monoxide, carbon dioxide, oxygen, hydrogenf would take place with the others?

What

reactions

7. How would you distinguish an ammonium salt from one of potassium or sodium? How distinguish between a potassium
salt

and a sodium

salt?

CHAPTER XXXI.
THE ALKALINE-EARTH METALS.
429.

The Group. -- The


"

"

alkaline-earth

"

metals

calcium family ") form a part of the second periodic group, and are intermediate between " " earth the alkali metals and the metals, such as
(also called the

Element.

CALCIUM.
include
it

393

with them in this chapter. The metal belongs in this group. Magnesium reacts with water at 100 C.; the others even at the

radium

also

The hydroxides of these ordinary temperature. metals are strong bases, and their salts with strong acids are neutral. The table shows that the properties
of the

members

of the

group and of their compounds,

vary in the order of the atomic weights.

its

Calcium does not occur free, but 430. Calcium. are found in large quantities. The compounds
is

most abundant
spar,

the carbonate,

CaCO

this occurs

as limestone, marble, chalk, cole-

and
4,
,

coral.

The

sulphate,

CaSO

the

phosphate,
fluoride,

Ca 3-

(P0 4 ) 2

and the

CaF

2,

are also important minerals.


Calcium
is

white, metallic luster.

a crystalline solid with a It is a little


it

harder than lead. With water

reacts

as sodium does, but less vigorously. Beyond being covered with a thin
film of oxide,
it

does not react with

dry
it

air at the

ordinary temperature.

At 760
takes

C., its
fire,
.

melting temperature, giving a mixture of CaO


obtained by the eleccalcium chloride
FIG.
83.

and Ca 3 N 2 Calcium
trolysis of
(Fig. 83).

is

fused

forms the anode.

The vessel holding the chloride is of carbon, and The calcium chloride at the bottom of the

394
anode
liquid
is

THE ALKALINE-EARTH METALS.


kept cold and solid by flowing water. That above is kept melts at 719 C.) by the resistance of the current. The

(it

cathode is a copper or iron rod (R), which dips into the melted calcium chloride. As the calcium is liberated, it rises to the top,

and

collects

on the cathode.

The cathode

is

raised

by the screw

(), so that the accumulated metal is gradually raised out of the melted bath. Sticks several feet long are thus obtained. Calcium
is

alcohol as well as with the water.

not used for dehydrating alcohol because it reacts with the The calcium hydroxide and

alcoholate formed are insoluble in the alcohol.

431. Calcium Oxide.

Calcium oxide
is

(lime,

or

made by heatquicklime) ing calcium carbonate, e. g., limestone, above 600 C.


CaC0 3
If carried

CaO+C0

out in a closed
is

vessel, the reaction

re-

versible

(cf.

243).

On

commercial,

scale, the lime-

heated in a large furnace, called a lime-kiln


is

stone

(Fig. 84).

The
FlG.
84.

construction of a
is

modern

lime-kiln
It

shown

in the figure.

consists of a long shaft of brick or limestone blocks, and is charged with limestone from the top (E). number of fire-boxes (F. B.) are built around the lower part of the and the hot

shaft,

gases from the fires enter the shaft, and cause the dissociation of the limestone. This is the " long-flame " process. The effi-

CALCIUM CHLORIDE.

395

ciency of the operation depends on the removal of the carbon dioxide as rapidly as it is formed. In this way the reverse action

The lime is removed at the bottom (D). a white, amorphous solid, fusible only at the temperature of the electric furnace. It is used in the lime light ( 55). When treated with water, it gives " slaked lime," a soft, dry powder. The reaction is a reversible one:
is

prevented.

Lime

is

CaO+H
Much
heat
is

evolved in slaking lime.

Ca(OH) 2 As a
.

result,

and warehouses containing it are often set on fire. Lime to remove water and carbon dioxide from gases (cf.

leaky cars is used


297).

When

exposed to the

air, it

forms air-slaked lime, a mixture of

the hydroxide and carbonate.

432. Calcium Hydroxide.

Calcium hydroxide

is

not very soluble


lime-water.

(cf.

"

Milk

of lime

429, Table). "


is

The

solution

is

lime-water with un-

dissolved calcium hydroxide.


Uses.

Lime

is

uses are: to prepare

generally slaked just before it is used. Some ammonia (cf. 203), the hydroxides of sodium

122 and potassium (cf. 412 and 421), bleaching powder (cf. and 438), chlorates (cf. 331), glass, mortar, and cement (cf. 436); to purify sugar and illuminating gas (cf. 297) to remove hair from hides; to soften wdter (cf. 435); to extract metals from their ores; as a disinfectant and white-wash, and in the making
;

of candles.

Calcium chlo433- Calcium Chloride (CaCl2 ). ride is usually made from calcium carbonate and hydrochloric acid

The anhydrous substance 277). 200 at (made by heating C.) is very deliquescent, and dissolves in water with evolution of heat. It is used
(cf.

as a drying agent

(cf.

90).

396

THE ALKALINE-EARTH METALS.


.

in water

The hydrate, CaCl 2 6 H 20, absorbs heat when dissolving (cf. 88), and when mixed with ice or snow may produce
48
C.

a temperature of
chloride freezes so
it is
(cf.

concentrated solution of calcium

much

lower than one of sodium chloride that

often used instead of brine as the cold bath in ice factories


207).

As already 434. Calcium Carbonate (CaCO 3 ). stated (cf. 285) calcium carbonate occurs in many forms and widely distributed. Limestone, chalk,
and marble are found in large masses. Aragonite crystallizes in a form different from that of the other varieties, but has the same composition.
calcite,
gray,

Limestone the most abundant form of calcium carbonate, is and often contains small crystals, but is always mixed with clay and other impurities. Limestone containing much Marl is used in making cement. Limestone is clay is marl.
,

used as a flux

(cf.

482) in smelting iron, as a source of lime,

and as building-stone.

penters use it for marking. as a source of lime, etc.

Chalk is used for making lime. CarMarble is used for building purposes,

435. Calcium Sulphate

(CaSO 4 ).

Calcium
.

sul-

phate occurs principally as gypsum, CaSO 4 2 2 0. Alabaster is a granular form of gypsum. Crayon
contains gypsum.

When gypsum is heated to 120 to 130 C. it loses about three-fourths of its crystal water, and forms the white powder known as Plaster of Paris.
2

CaS0 4 (H 0) 2
2

(CaS0 4 )2H 2 0+3


plaster of

H 0.
2

gypsum

Paris

CALCIUM SULPHATE.
When
it

397

powder is mixed with enough water to form a paste expands, and hardens to a mass with a smooth surface. Bethis
is

cause of these properties plaster of Paris


rigid surgical bandages, as a wall finish,

used to

make

casts,

and as a cement.

The

union of the powder with water produces the crystalline compound.

(CaS0 4 ) 2H 20+3

>

CaS0 4 (H 20) 2

Stucco consists of plaster of Paris, stone, and glue. Calcium sulphate is slightly soluble; Softening of Water. water containing it is permanently hard (cf. 70). Permanent hardness may also be due to magnesium sulphate or chloride,
calcium chloride, etc. If water contains only permanent hard" breaking," may be accomplished by ness, the softening, or the use of a soluble carbonate, such as Na 2 C0 3 or (NH 4 ) 2COs
(cf.

414 and 427).

CaSQ4 +Na C0 3
2

CaC0 3 1 +Na S04


2

If

"

broken

the water contains only temporary hardness, it may be " by boiling (cf. 284), or by means of the theoretical
of lime.

amount

Ca(HC0
If
4

3) 2

+Ca(OH)

CaC0

+2 H 0.
2

NH OH may be used.
soluble

the water contains both kinds of hardness, NaOH or This reacts with the carbonic acid of the

bicarbonate, thus releasing the insoluble

normal carbonate.
is

The

(NH4 ) C0 which the permanent hardness as CaC0


Na C0
2 3,

or

3,

formed, precipitates

3.

(1)

(2)

Ca(HCO) 2 +2 NH4 OH CaS0 +(NH C0


4 4) 2 3

CaC0 J + (NH C0 3 +2 H 20. CaC0 1 +(NH4 ) S0


3 4) 2 3 2 4.

When
(cf.

the hardness

is

due to magnesium

salts,

sodium com-

pounds, not
442).

ammonium compounds,

are used to soften the water

398
The
is

THE ALKALINE-EARTH METALS.


objection to hardness in a water used for generating steam

partly the fact that deposits of limestone, gypsum, etc., accumulate on the inside of the boiler (" boiler scale "), and cause

chlorides,

waste of heat; but if the water contains calcium or magnesium the hardness is much more serious, for these salts,
" "
pits

especially the latter, are hydrolyzed at the high temperature of

the boiler, producing hydrochloric acid, which


(cf.

the boiler

442).

Normal Phosphate, Ca 3 (PO 4 ) 2 calcium phosphate occurs as phosphorite; combined with calcium chloride or fluoride it forms apatite,
436. Calcium
.

CaCl2

(or

CaF

2)

Ca3 (P04 ) 2

Important deposits

of

(" rock phosphate ") are found in In 1910 Florida, South Carolina, Tennessee, etc. the United States produced 2,655,000 long tons of rock phosphate. Most of it was used as fertilizer

these minerals

Calcium phosphate 358) constituent of bones (cf. 343).


(cf.
.

is

the chief inorganic

and Concrete. When a and water is exposed to the In the air, it sets," i. e., becomes dry and hard. hardening, water escapes, and carbon dioxide unites
437. Mortar, Cement, thick paste of slaked lime "

with the slaked lime.


Ca(OH) 2 +H 2 C0 3
"

CaC0 +2
3

While setting," mortar contracts. In mortars and cements this contraction is overcome by the use of sand. Sand also makes
mortar porous, so that carbon dioxide can penetrate farther, and moisture can escape more easily. The sand should be sharp, so that it will become firmly imbedded in the crystals of calcium

-OTHER CALCIUM SALTS.

399

carbonate as they are formed. Freshly plastered walls remain moist for some time, because the exchange of carbon dioxide
for water is slow.

When limestone and clay (aluminum silicate; limestone or containing naturally the right proportion cf. 393), of aluminum silicate, are heated together, there is formed a
Cement.
cement. This slakes slowly, and without much heat evolution, and has the valuable property of hardening under water. Hence it is called hydraulic cement. Portland cement is made by heating to a high temperature an artificial mixture which contains the required proportions of calcium oxide, aluminum oxide (A1 2 3 ), and silica (Si02), and then grinding the mass to a fine powder. Limestone, or marl, and shale, or clay, furnish the necessary constituents. Blastfurnace slag
(cf.

482) forms with limestone a similar mixture.

Cement probably consists of a mixture of calcium silicate (SiOz. 3 CaO) and calcium aluminate (A1 2 3 3 CaO). Its harden.

ing

is,

apparently, due to the union of

its

components with water

of crystallization.
is a mixture of water, cement, sand, and hardens into a compact mass, and thus makes an excellent material for sidewalks, foundations and floors of

Concrete.

Concrete
It

crushed stone.

and for structures under water, such as bridge-piers Reenforced concrete is concrete and the walls of dams. rods of iron or steel, which are imbedded in it. strengthened by In 1901 It is used on an enormous scale for building purposes.
buildings,

the United States produced about 20,000,000 barrels of cement;


in 1910, almost 77,800,000 barrels.

438. Other
,

Calcium

Salts.

CaOCl2 has been


it

described in

Bleaching powder, 122 and 329. If


,

were a mixture of Ca(OCl) 2 +CaCl 2 alcohol would


it.

extract calcium chloride from


occur,
it is

Since this does not


salt,

assumed to be the mixed

CaOCl2

400
Calcium
glass
(

THE ALKALINE-EARTH METAJ.S.


silicate,

CaSi0 3

is

a constituent of rocks and of


solutions of sodium silicate

394).

It

is

made by mixing
,

and calcium chloride, and by fusing quartz with limestone. Calcium carbide, CaC 2 is made by heating lime, or limestone,
with
coal, or coke, in

the electric furnace.

CaO+3 C
The pure substance
mercial product
giving acetylene
is
(cf.

CaC

+CO T

The comis a white, crystalline solid. dark, because impure. It reacts with water,
295).
is

Calcium sulphide, CaS,

a white, soluble solid

made by

It is a by-product in reducing calcium sulphate with carbon. the Le Blanc soda process (cf. 414). After the commercial

sulphide has

hence

been exposed to sunlight, it phosphoresces; used in making luminous paints for match-boxes, Barium and strontium sulphides have similar clock-faces, etc. The properties. phosphorescence is due to minute amounts oj
it

is

bismuth compounds, etc.


phoresce.

The pure

sulphides do

not phos-

Calcium Cyanamide, CaN. CN, is formed by the reaction between calcium car bide, heated to white heat in an electric furnace, and nitrogen, which is conducted over it.

CaC
The product
soil
is

+N
to

CaN.

CN+C.

used as a
it

and

air

change

fertilizer. The water and oxygen of ammonia and nitrates, both of which

contain nitrogen in excellent form for plant food.

439. Strontium.

The compounds
are less

of-

strontium resemble those of calcium, but


useful.

abundant and

Strontium
its chloride,
,

is

like calcium.
.

It

is

made by

the electrolysis of

SrCl 2

given the hydroxide, Sr(OH) 2 and hydrogen.

With water it The oxide is pre-

BARIUM.
,

401

pared by heating the nitrate, Sr(NO 3 ) 2 (c/. 230). The carbonate is decomposed by heat with great difficulty (see table, 429).

The oxide reacts with water and with carbon dioxide as lime does. " The sulphate is " insoluble (see table), but the carbonate is
still less

soluble;

hence the former

is

converted into the latter

when

it is

boiled with a soluble carbonate.

SrS0 4 +Na2 C0 3
Strontium
salts

SrC0 3

+Na S0
2

4.

The

nitrate
is

hydroxide

impart a red color to the non-luminous flame. used to prepare red lights and fireworks. The used in refining beet-sugar.
is

440. Barium.

Barium

is like

calcium and strontium.

It

is

electrolysis of its chloride,

BaCl 2

Barium occurs

obtained by the in nature as


.

witherite (BaC0 3 ) and as heavy spar, or barite, BaS0 4 Heavy spar has a specific gravity of 4.48. The oxide (BaO) is made by decomposing the nitrate, Ba(N0 3 ) 2 and by heating the carbon,

ate with charcoal.

BaC0 +C
3

BaO+2 CO
"

Note that
'

this

is,

essentially,

removing the

C0

from the

oxide unites with water, forming the This crystallizes from water as Ba(OH) 2 hydroxide, Ba(OH) 2 " " 159 and 283). Its solution is 8 2 O. (c/. baryta water

sphere of action.'

"

The

The chloride

It may be made crystallizes as BaCl 2 2 H 20. from the oxide, sulphide, or carbonate and hydrochloric acid. It is also made by heating the sulphate with charcoal and
.

calcium chloride.
(1)

(2)

BaS0 4 +4 C (BaS) +CaCl 2

(BaS)+4 CO T BaCl 2 +CaS.

(cf.

254 and 438).

402

THE ALKALINE-EARTH METALS.


,

Barium peroxide, Ba0 2


to dull redness in the
air.

is

formed when the oxide


is

is

heated
(

It

used to prepare oxygen


to the

22)

and hydrogen peroxide ( 339). Barium salts impart a green color


before the flame test
is

Bunsen flame.
c.p.

They

should be moistened with concentrated


applied.

hydrochloric acid Barium nitrate and the chlorate


lights

[Ba(C10 3 ) 2

are used in

making green

and

fireworks.

to the insolubility of barium sulphate, soluble barium salts are used to test for soluble sulphates, i. e. } ionic SC>4.

Owing

441. Magnesium. Magnesium occurs in the Stassfurt deposits as chloride and sulphate (cf. 420).
It occurs also in dolomite

nesite

(MgC0

3 ),

and

in

(MgC0 CaC0 ), magmany magnesium silicates,


3.
3

such as soapstone, meerschaum, serpentine, and asbesThe metal is prepared by the electrolysis of the mineral carnallite, MgCl 2 KC1. 6 2 O.
tos.
.

Magnesium

is

a silver-white metal with a high

luster.

It

is

light (see table) ,

and oxidizes slowly


cf.

in ordinary air.

It

burns

in air with a flame of dazzling whiteness, giving the oxide

and the nitride (Mg3 N 2


alkali

188).

(MgO) Magnesium does not react

with water at the ordinary temperature (difference from the and alkaline-earth metals, proper), but it burns vigorously when heated in steam. The light from burning magnesium is

admirably adapted for photography; hence a mixture of the powdered metal and potassium chlorate is used for flash lights. Magnesium is also used for signal lights and in fireworks.

Magnesium Compounds. Magnesium oxide is formed when the metal (magnesia) burns, and when the hydroxide and carbonate are heated. It
442.

RADIUM.

403

reacts slowly with water to give the insoluble hydrox-

Magnesia is very refractory, i. e., ide, Mg(OH) 2 hard to melt; hence it is used in making crucibles,
.

cupels, fire-brick,

and parts

for electric furnaces.


.

Magnesium
6

chloride

H 0)
2

When
(1)
(2)

forms deliquescent crystals (MgCl 2 these are heated, the chloride is hydrolyzed

(cf.

435).

MgCl2 MgCl 2

H
2

>

MgCl 2

H 0+5 H 0.
2
2

MgO+2
,

HCJ.

is

found in

Magnesium sulphate, MgS0 4 is called "Epsom many springs, and in kieserite (MgS0 4

salts."

It
etc.

H 0),
2

magnesium sulphate
from
it (cf.

Kieserite unites with water to give of commerce.


419).
is

MgS0

4.

H 0,
2

which
is

is

the

Sodium sulphate

made
salts

Magnesium hydroxide
by sodium hydroxide;

precipitated from

magnesium

but only incompletely by ammonium

hydroxide, owing to the reverse action.

MgCl 2 +2
If

NH OH ;=Mg(OH) +2 NH C1.
4 2

an excess of an ammonium
is

salt is present,

magnesium

not precipitated at all by ammonium hydroxide, neither is magnesium carbonate precipitated, under the same Normal 435). conditions, by ammonium carbonate (cf. hydroxide

magnesium carbonate
produced by
alkali

so readily hydrolyzed that the precipitate carbonates and magnesium salts always " " consists of the basic carbonate. magnesia alba is Thus,
is
.

Mg(OH) 2
443.
were,

MgC0

3.

Radium.
in the last series of the periodic table
(

The elements
until

383)
of

1898,

thorium and uranium.

The discovery

404

THE ALKALINE-EARTH METALS.


in the following

radium came about


in

way:

1896, that

when uranium compounds

(e. g.,

Becquerel found, pitchblende, a

uranium ore) are placed near photographic plates which are protected from light, they affect the plates like light itself. He ascribed the effect to active rays ("Becquerel rays") given off

by the uranium. The simplest way to test for the presence of these rays, and for their amount, is to hold the material to be
examined near a charged, insulated electroscope. If the material " is radio-active/' the air becomes a conductor, and the electroThe time required measures the " radioscope .is discharged. " of substance. Professor and Mme. Curie, of Paris, the activity removed the uranium compound from pitchblende, and found
that the residue

was

still

very active.

By

separating
of

it

carefully
chloride,

into its parts they obtained a small

amount

barium

and by analysis of
salt,

this they secured a minute quantity of a

new

radium

chloride.

This was more than 1,000,000 times as

The properties of radium compounds active as pitchblende. place the element with the alkaline-earth metals, which are bivalent. The equivalent weight of the element was found, by
analysis of the chloride, to be 113.2; hence the atomic weight is In the periodic table it fills the space below barium. 226.4.

Radium compounds have

the formulas

RaCl 2 Ra(OH) 2
, ,

etc.

All give off heat constantly, are self-luminous, In 1910 radium carbonate, radio-active.

and are strongly RaC03 was treated

with hydr azoic acid

(HN

Ra(N 3 ) 2

When
was

this

radium and nitrogen.


like its salts,

and converted into the hydrazoate, was heated in a vacuum, it broke up into The radium had a metallic luster, and,
3 ),

radio-active.
of radio-activity are explained

The phenomena

by the

as-

sumption that the rays consist of particles, called electrons, or corpuscles, which are given off by the radio-active substance.

Radium compounds

also

give off a gaseous material

called

condensed by liquid air. It belongs to the argon family, has the atomic weight 222.4,
niton.
is

radium emanation, or

This

EXERCISES.

405

and is in the same periodic series with radium, etc. When niton is examined with the spectroscope, it shows the spectrum of helium. Thus it appears that radium is constantly being formed " by the decay" of uranium, that niton is formed by the decay of radium, and that niton breaks down into helium, the element

The discovery that niton gives helium belongs to Sir William Ramsay, of London. He found, further, that when cupric nitrate is enclosed
of lowest atomic weight in the argon family.

with niton, some lithium nitrate is formed. The copper is said " " to lithium, the element of lowest atomic to be degraded
weight in the alkali family. Ramsay has also found that the elements of the carbon family, i. e., thorium, zinc, titanium, and " " " emanation " into carbon. by the degraded silicon, are

We must conclude, therefore, that some of the elements decompose, giving others of lower atomic weight. This does not do away with the conception of the atom, but, on the contrary, enlarges
it.

444. Exercises. 1. How would you prove that some calcium

nitride

is

formed
is

when calcium burns in the air? 2. Magnesium liberates the hydrogen

of

ammonia;

ammonia, therefore, an acid? 3. Would you expect barium sulphate to be


centrated sulphuric acid write the equation.
(cf.

soluble in con-

267)?

Name

the product, and

Does carbonic
equation.

acid react with barium carbonate?

Write the

4. Write the equation for the preparation of the oxide of each of the alkaline-earth metals from its nitrate. Name these oxides in the order of their reactivity with water, beginning

with the most active. 5. From the relative


sulphate
(cf.

solubilities of
viii)

Appendix

barium carbonate and would you expect to change the

406

THE ALKALINE-EARTH METALS.


former by boiling
it

latter into the

with sodium carbonate

solution?

How

could you separate a mixture of strontium and

barium sulphates? 6. How could you separate the metal ions in a mixture of strontium chloride and magnesium chloride? Barium nitrate and potassium nitrate? Write the equations. 7. Write the partial and complete equations for the formation of magnesia alba from magnesium chloride.

CHAPTER XXXII.
ZINC,
445.

CADMIUM, AND MERCURY.


The elements
zinc, cad-

The Zinc Group.

mium, and mercury are members


of the periodic system.

of the second group

more closely related cium group proper. much alike, and are usually found together in nature; but mercury differs from them in some important
respects.

They are, however, much to magnesium than to the calZinc and cadmium are very

three contain one

In the vapor state the molecules of atom each (cf. 142).

all

Zinc generally occurs in combination 446. Zinc. as the sulphide, ZnS, the carbonate, ZnCO 3 and the The metallurgy of zinc is simple. silicate, Zn2 SiO 4
,
.

Its ores are generally roasted to convert

them

into

oxide,

ZnO, and the oxide

is

reduced by

charcoal.

The reduction

of zinc oxide takes place in retorts or furnaces;

from these the metal distills over into condensers. At first the vapors condense as a powder (zinc dust); afterwards the metal condenses as a liquid, and is cast into plates and bars. The Pure zinc is zinc thus obtained (called spelter) is not pure.
obtained by the electrolysis of zinc chloride.

Zinc 447. Properties. lustrous metal. In dry air


407

is it

a white, hard, and does not change; but

408

ZINC,

CADMIUM, AND MERCURY.

ordinarily its luster is soon dulled by a covering of basic carbonate. At the ordinary temperature, zinc
is brittle;

but between 100 C. and 150 C.

it

can be

rolled into sheets


it is

and drawn

into wire.
it

At higher

can be powdered. temperatures Zinc melts at 420 C., and boils at 920 C. When heated much above the melting-point, it burns to zinc oxide. Water does not affect the metal, even at
so brittle that

Hot solutions of alkali hydroxides react 100 C. with it, forming zincates and hydrogen (cf. 57, 388,
and
474).

Zn+2

KOH

>

K Zn0 +H
2

2.

Commercial zinc reacts readily with all the ordinary acids; but the pure metal requires a catalyzer, such as copper or platinum (cf. 47.)
Zinc is used for the positive plates of 448. Uses. electric batteries and in alloys, e. g., brass (cf. 458),

German

silver, etc.

Galvanized iron is iron coated with zinc by dipping Galvanized iron resists it into a bath of molten zinc. the action of air and moisture better than tinned iron.
It is

used for wire netting, corrugated roofing, gutters,

water-tanks, etc.

Compounds. zinc compounds are the sulphate, and sulphide.


poisonous.

449. Zinc

Among
oxide,

the important

Soluble

hydroxide, chloride, zinc salts are

MERCURY.

409

Zinc oxide, ZnO, can be made by burning zinc, and by heating When hot it is yellow; the carbonate or nitrate (cf. 230). when cold, white. It is sold as the pigment, zinc white.

Zinc hydroxide, Zn(OH) 2 is precipitated when zinc salts It redissolves in an excess of react with soluble hydroxides. alkali hydroxides, giving zincates.
,

Zinc chloride, ZnCl 2


with hydrochloric acid
solid that fuses readily
is

may
and

(cf.

47).

be formed by treating the metal It is a white, deliquescent


without decomposing.
It

distills

usually cast in sticks.


,

Zinc sulphate, ZnS0 4 is formed from the metal and dilute sulphuric acid. Large quantities are made by roasting the natuH sulphide, ZnS, and extracting with water.

ZnS+20
.

ZnS0 4

From water the sulphate separates as transparent crystals of " white 2 0. vitriol," ZnS0 4 7 Zinc sulphide, ZnS, separates as a white precipitate when an alkaline sulphide is added to the solution of a zinc salt. Zinc " " sulphides moderately insoluble sulphide belongs to the

(cf.

255).

It

is

because of the reverse action.


tated at
all.

precipitated only partly by hydrogen sulphide, If acid is present, it is not precipi-

ZnS0 4 +H 2 S

ZnS+H S0
2

4.

Cadmium is similar to zinc, 450. Cadmium. at 749 C., and is used in makboils 320 at melts C.,
ing

some

alloys

(cf.

374).

The

sulphide,
is

CdS, forms

a beautiful, yellow pigment, which


alkali sulphides
(cf.

not soluble in

365, 369,

and

516).

Mercury, or quicksilver, occurs 451. Mercury. native in some of its ores; but the principal source of
it

is

cinnabar,

HgS.

Cinnabar

is

mined

chiefly in

410

ZINC,

CADMIUM, AND MERCURY.

Spain and California; recently deposits have been found in Texas. Mercury is obtained from its ore

by

The sulphur passes off as sulphur the mercury vapors are condensed. while dioxide;
roasting.

Mercury is a white, 452. Properties and Uses. as heavy as water, It is 13.6 times lustrous liquid. and at 357 C. boils solidifies at -39.5 C.,
Mercury does not react with hydrochloric acid nor with cold sulphuric acid. Hot, concentrated sulphuric acid attacks it (cf. 265) so does nitric acid. If the nitric acid is dilute and cold, and the mercury is in
;

excess, the salt


if

formed

is is

mercurous

nitrate,

HgNO

used, and the mercury is mercuric used nitrate, Hg(NO 3 )2, is up, completely are nitrates formed. Both white, crystalline solids.

the concentrated acid

Mercury vapor and


poisonous.

soluble

mercury

salts are

very

Mercury is used in extracting gold and silver from their ores, in amalgamating battery zincs, and in making thermometers,

barometers, air-pumps, percussion caps, etc.

453. Mercury Compounds. Mercuric oxide, HgO, also known as "red precipitate," may be made by long heating of the metal almost to its boiling temperature in contact with air. It is usually prepared by heating Another form the nitrate Hg(N0 3 )2 (cf. 449; zinc oxide). is yellow in color; this is prepared by adding an alkali to the
solution of a mercuric salt.

NaOH+Hg(N0

3; 2

NaN0 +HgO+H 0.
3 2

MERCURY COMPOUNDS.

411

the oxides.

The hydroxides of mercury lose water spontaneously, giving The effect of heat upon the oxide is described in 16. Mercurous oxide, Hg20, is formed when an alkali is added

to a mercurous salt.

Mercurous chloride, HgCl, is known as calomel, and is an important medicine. It is precipitated when a solution of a chloride is added to a solution of a mercurous salt.
It
is

commonly made by subliming a mixture

of

mercury and

mercuric chloride,

Hg+HgCl
The reverse
must be kept in the dark, or Mercuric chloride HgCl 2
,
,

2HgCl.

action takes place in the light; hence calomel it will contain corrosive sublimate.

limate.

It is

is commonly called corrosive submade by subliming a mixture of mercuric sulphate

and sodium

chloride.

HgSOH-2 NaCl
Mercuric chloride
in water,
is

HgCl 2 +N a2S04

and very poisonous.

a white, crystalline solid; it is easily soluble It is used extensively in surgery

antiseptic action. 181 and 516.

(usually one part in 1,000 parts of water) because of its powerful For its reduction by stannous chloride cf.

Mercuric chloride and nitrate react with ammonium hydroxide, giving white precipitates of HgNH 2Cl and HgNH 2N0 3
,

respectively.

They

are

"
3

mercur-ammonium "
2

salts.
4

HgCl 2 +2
Mercurous

NH

HgNH Cl j +NH C1.


nitrate give corresponding salts, but

chloride

and

they are black, because mixed with finely divided mercury.


2 HgCl-f-2

NH

Hg I +HgNH

Cl

+NH C1.
4

Mercuric sulphide, HgS, occurs as cinnabar ( 451), a red, The sulphide may be made by rubbing tocrystalline solid. and mercury sulphur, and by passing hydrogen sulphide gether

412

ZINC,

CADMIUM, AND MERCURY.


but when
is

into the solution of a mercuric salt.

sulphide will
crystals.

be black;
is

The

red product

In both cases the mercuric is sublimed it yields red " Chinese vermilion." the pigment,
it

not affected by dilute acids. Mercurous is precipitated from mercurous salts by hydrogen sulphide but decomposes spontaneously, giving mercuric sulphide,

Mercuric sulphide

sulphide and mercury.


iodide solution

Mercuric iodide, HgI 2 is precipitated when a potassium An excess of is added to one of a mercuric salt.
,

potassium iodide redissolves the precipitate, owing to the formation of 2 HgI4 which is soluble. Mercuric iodide is also made by triturating a mixture of potassium iodide and mercuric

chloride, or of
is

mercury with an excess of

iodine, in

a mortar.

It

a bright-red powder, soluble in hot alcohol and in ether. When heated, the dry powder gives a yellow sublimate; this reverts to the red form, when rubbed, with evolution of heat
(cf.

249).

Mercuric iodide

is

used as an antiseptic, replacing

the chloride.

Mercurous iodide, Hgl, is a yellow-green powder obtained from a mercurous salt solution and potassium iodide, also by grinding iodine with the calculated amount of mercury. It is insoluble in alcohol and in ether, and is changed by the light, and by potassium iodide solution, into the mercuric salt and
mercury.

Mercuric fulminate, Hg(ONC) 2 is used for percussion caps. Sodium amalgam was described in 403 and 411. Tin amalgam was formerly used in making mirrors. Zinc amalgam " is formed on the positive plate when battery zincs are amalSeveral have been used for soft gamated." amalgams fillings
,

by

dentists.

454. Exercises.
i.

Write equations, partial and complete, for the following

reactions:

EXERCISES.
(a)
(6)

413

Zinc sulphate solution with excess of sodium hydroxide. Preparation of mercury from cinnabar, and of mercurous and mercuric nitrates from mercury. (c) Preparation of mercuric oxide from the nitrate, by heat.
(d)

Preparation of

cadmium

oxide, sulphate,

chloride,

and

sulphide.
(e)

Mercurous nitrate solution and hydrogen sulphide.


Mercuric sulphate solution with potassium iodide (excess). Action of mercurous iodide with potassium iodide. Action of sodium amalgam with water.

(/)
(</)

(h)
2.

Give all the changes that would take place if sodium zincate solution were treated with hydrochloric acid, drop by drop, until there was an excess.
3. Give characteristic tests for mercury, zinc, and cadmium, by which you can distinguish between them. 4. How could you separate a mixture of mercurous, mercuric

said zinc

ions, so as to get

each in the form of a precipitate?

Write the equations.

CHAPTER

XXXIII.

COPPER, SILVER, AND GOLD.


455. Relation of Copper, etc., to the Alkali Metals. -Copper, silver, and gold are in most respects

from the other members of the first periodic the alkali group, but are related to these elements much as zinc, cadmium, and mercury are metals
different

by pure air; hence they occur native as well as combined with other elements. Because they occur native all three have been known for thousands of years, while none of the alkali metals was known until 1807.
and Metallurgy of Copper. Copper is abundant and widely distributed. It occurs native, especially in the Lake Superior region, and in combination as ruby copper, Cu2 0; malachite, CuC0 3 Cu(OH) 2 chalcocite, Cu2 S; and copper Bornite is (Cu2 S) 3 Fe2 S 3 azupyrites, Cu2 S. Fe2 S 3
456. Occurrence
. ;
.
.

related to the calcium group. They are not changed by water or

rite,

Cu(OH) 2

CuCO

3.

Of the world's supply of copper, the United States produces

more than

half: 504,000 tons in 1910.

is obtained by crushing the ore, washing away the lighter particles, and smelting and refining the concentrated " mineral" Lake Superior ore has from 0.75% to 5% of copper.

Native copper

414

OCCURRENCE AND METALLURGY.

415

Oxide, hydroxide, and carbonate ores are smelted with coke

One fusion often yields a 96% copper. ores contain iron, as well as lead, arsenic, usually Sulphide etc. Except for ores of very low grade, the processes are as follows:
in blast-furnaces.
1.

The

ores are concentrated


(cf.

then roasted

252), to

by crushing and washing, and are remove most of the sulphur. The

sulphur dioxide produced may be used for sulphuric acid. Part of the iron becomes iron oxide, and most of the copper, copper oxide.
2. The roasted ore is then mixed with coke, to reduce the copper oxide, and with acid silicates, to unite with the iron oxide. The mixture is smelted in a blast-furnace (cf. 482; P'ig. 88).

Iron

silicate is

formed as a

light slag that

can be drawn

off,

while

the heavy liquid below it consists largely of the sulphides of iron and copper. It contains from 30% to 60% copper, and is
called
3.

" matte."

third operation is the formation of " blister copper," " of the matte in a Bessemer oxidation the converter," by like the one used in making steel (cf. 487; Fig. 90). In the " " a blast of hot air, sometimes containing sand, is converter

The

up through the melted matte, and removes most remaining sulphur, arsenic, antimony, lead, and iron, as
forced

of the
oxides.

The volatile scum on the


converter
is

oxides escape, while the non-volatile ones form a surface, or unite with the silica, with which the

lined, to

form

silicates,

or slags.

Some

of the copper

oxide formed reacts with cuprous sulphide:

Cu 2 S+2 CuO
Occluded sulphur dioxide
(cf.

Cu+S0

when the copper


4.

solidifies,

gives

53 and 463), which escapes the metal a characteristic

blistered appearance.

The

air-blast of the converter oxidizes

some

of the copper.

The

process called

"

poling

"

consists in reducing the copper

416
oxide

COPPER, SILVER,
by
stirring the

AND

GOLD.

melted

blister

furnace
"

(cf.

462;

Fig. 86) with long poles of


is

copper in a reverberatory " " wood. green


of thick plates called

Finally, the product

cast in the

form

anodes," and refined by electrolysis.


5.

sists in

Refining of Copper. The refining process (Fig. 85) conmaking the thick plates of impure copper the anodes

of electrolytic cells containing cupric sulphate solution; while a thin plate of pure copper forms the cathode. The anode wastes

away, and

Many

its copper is deposited, in pure form, upon the cathode. copper ores contain small amounts of gold and silver,

FIG.

85.

and these accompany the copper up to the refining process. In the electrolysis, however, the precious metals, along with some cuprous sulphide, lead, and bismuth, are left in the refining tanks " as mud." This is collected, and the gold and silver are extracted from it.
457. Properties. Copper has a red color, and is ductile and malleable. It melts at about 1080 C.,

while silver melts at 954


is

C. and gold at 1060 C. the best conductor of electricity known, exCopper iron is the only metal having greater cept silver;
tensile strength.

The

specific gravity of

copper

is 8.9,

COPPER COMPOUNDS.

417

In the atmosphere copper becomes coated with the basic


carbonate
(cf.

sulphuric acid
respectively.

456). The action malachite, upon copper has been discussed

of nitric acid
in

and

227 and 265,

Hot, concentrated hydrochloric acid reacts slightly Dilute acids giving cuprous chloride and hydrogen. act on it slowly, in the presence of air, giving cupric salts. The

with

it,

sulphate

is

made

in this

way.
2 4

Cu+0+H SO
etc.,

CuS0 4 +H

0.

Copper may be separated from solutions and by electrolysis.

of its salts

by

zinc, iron,

Copper is used as an electric con458. Uses. as ships' sheathing and bolts, and for electrical ductor,
apparatus, utensils, coins, boilers,
used, also, in copper-plating
stills,

etc.
,

It is

and

electrotyping

and as

a part of
copper.

many

alloys.

Brass usually contains

28%

to

34%

zinc

and the remainder

Bronze contains copper, zinc, and tin. Gun-metal is about 90% copper and 10% tin. Bell-metal consists of copper, about 75%, and

tin,

25%,.
zinc,

German silver is, approximately, 50% 20% nickel. Aluminum bronze is copper with 5%
It has the color of gold,
easily.
is

copper,

30%

and

to

hard and

elastic,

10% of aluminum. and does not tarnish


is

Aluminum

containing

3%

of copper

whiter than pure

aluminum.

459. Copper
iron, etc.,

Compounds.
series of
(cf.

forms two

Copper, like mercury, compounds: cuprous and

cupric
are:

compounds

111 and 169).

Examples

418

COPPER, SILVER,

AND

GOLD.
Cupric
chloride,

Cuprous chloride, CuCl or Cuprous oxide, Cu 2 0. Cuprous sulphide, Cu 2S.

Cu 2Cl 2

CuCJ 2

Cupric oxide, CuO.


Cupric sulphide, CuS.

In the cupric compounds copper is evidently bivalent. If copper is bivalent in the cuprous compounds of the halogens, e. g., in cuprous chloride, the simpler formula must be doubled.

Cu
The
constitutional

Cl. Cl.

formula

will

then be

Cu
"

Cuprous oxide occurs naturally as ruby copper." It is formed as a black scale when the metal is heated in the air, and as a red precipitate when a solution of a cupric salt is heated
with the solution of an alkali in the presence of a suitable reducing agent,
e. g.,

grape-sugar,

C Hi
6

6.

Cuprous sulphide is made by heating copper with sulphur. Cupric oxide is formed by treating a boiling solution of a The blue cupric cupric salt with the solution of an alkali. hydroxide, Cu(OH) 2 which is formed if the solution is cold,
,

cannot exist in the boiling solution.

CuS0 4 +2

KOH

>

K S0
2

+Cu(OH) a
2

Cu(OH) 2

CuO+H 0.

Cupric sulphate pentahydrate is blue vitriol (cf. 88). The anhydrous salt is white. It dissolves in hot, concentrated sulphuric acid, and separates, when cold, in white crystals. Blue
vitriol is

used in making blue and green pigments, in copper-

plating, in preserving

wood, and for gravity batteries.

It

is

also used extensively in agriculture as a germicide

The Bordeaux mixture consists of A minute amount of cupric sulphate.


kill

and fungicide. calcium hydroxide and cupric

larger water animals,

and water reservoirs, and

sulphate, too small to able to destroy the algae of ponds so to purify the water.
is

SILVER.
Cupric sulphide, CuS,

419

is a heavy, black solid, precipitated cupric salts in solution are treated with hydrogen sulphide or with alkaline sulphides. Cupric salts react with excess of ammonia-water to give solutions of deep-blue color.

when

CuS0 4 +4
The deep-blue
ions,

NH

Cu(NH S0
3) 4

4.

color

is

due to the complex, bivalent, positive

Cu(NH

3) 4 .

object that is to be put into a bath of some copper salt in solution, and connected with the kathode of a battery or dynamo circuit (cf. Fig. 85). A bar of copper is used for the anode. The bar of copper is gradually used up, and copper is deposited upon the object to be plated. The bath does not deteriorate. 460. Copper-plating.
is

An

plated with copper

This process is used in making electrotype plates, either from An impression of the type or wood type or from woodcuts. cut is first made in plaster of Paris; this is covered with graphite

powder and placed in the copper-plating bath as the kathode. The plate produced is an exact reproduction of the type or woodcut from which the plaster impression was taken.
Silver is found native; also com461. Silver. bined with sulphur and with the sulphides of other

metals.
silver.

The lead ore, galena (PbS), usually contains The natural chloride, AgCl, is called " horn
of the world's silver is

silver."

Most

States, Mexico, Bolivia,

and

Australia.

found in the United The United

420
States

COPPER, SILVER,

AND

GOLD.

produced, in 1910, 57,137,900 ounces about one third of the world's supply for that year.
Silver 462. Extraction of Silver from its Ores. we from ores various its processes; by separated

is

shall

consider

only

two,

viz.,

the

Amalgamation

Process and

the Smelting Process.


consists in extracting the metal

The Amalgamation Process

with mercury, after a preparatory treatment. This treatment consists in crushing the ore, roasting it with salt to change the

FIG.

86.

REVERBERATORY FURNACE.
(The
fuel

The curved

burns at W; the substance to be heated is placed on the hearth B. roof A directs the hot gases of down upon B.)

sulphide into the chloride of silver, and then reducing the chloride to silver by means of water and iron. The mass is then mixed

with mercury, and the resulting amalgam

is

collected,

dried,

and heated

ready to be used again; the silver is then separated from whatever gold is present, as described at the end of this section. Silver ores usually contain lead, and Smelting Process.
in retorts.
distills off,
is

The mercury

and

lead ores often have enough silver to

pay

for its removal;

hence

PROPERTIES.
the reduction of the two metals
operation. The lead ore
is

421

carried out in a single smelting

is roasted to remove sulphur, and then reduced with coke in a blast-furnace. The silver and the gold present remain alloyed with the lead. The resulting crude lead (known as base bullion) is then heated in a reverberafory furnace (Fig.

and stirred frequently. The small quantities of copper, arsenic, and antimony present are thus oxidized, and are skimmed What remains is a mixture of from the surface as dross. Most of the lead is now removed by the lead, silver, and gold. Parkes Process. This consists in melting the metal in large iron pots, adding 1% to 2% of zinc and stirring. When the mixture is cooled slowly, an alloy of zinc, silver, and gold, with but little lead, comes to the surface, solidifies, and is skimmed off. If necessary, zinc is added a second or even a third time. The skimmings are then heated in graphite retorts (cf. 272) and the zinc is distilled off, condensed, and cast into slabs to be used again. The residue in the retort consists of lead, silver, and gold. The lead is now completely removed from the precious metals
86),
;

by

oxidizing

it

with hot

air in

a shallow furnace.

The

lead oxide

(litharge,

PbO)

flows off from the top of the furnace.

Gold is separated from silver by treating the mixture of these metals with nitric acid, or hot, concentrated sulphuric acid. The gold is not acted upon.
The sulphuric acid separation is carried out in iron The silver sulphate formed is treated, in solution, with
which precipitates
silver.

kettles.

copper,

This

is

melted and cast into

ingots.

of receiving

Silver is a white metal, capable 463. Properties. a mirror-like polish. It conducts heat
electricity better

and

malleable and ductile.

than any other metal, and is It melts at 954 C., and boils

422
in the

COPPER, SILVER,

AND

GOLD.

oxy hydrogen flame. Melted silver absorbs about twenty-two times its own volume of oxygen;

when

the
"

silver

solidifies,

the

gas

is

given
is
.

off

(" spitting

of silver).

quickly blackened by sulphur compounds (cf. 250) Hydrochloric acid does not attack it. Nitric acid and hot,

Silver does not tarnish in pure air, but

concentrated sulphuric acid act upon


copper.
464. Uses.
Silver
is

it

as

upon

used for coinage, tableware,

jewelry, ornaments, and mirrors, and for plating other metals. Pure silver is very soft, and is therefore al-

loyed with copper.


silver "),
fine is

The

silver coins of the

United
(" coin

States and of France contain

90%

silver

to be 900 fine. The grade 925 called "sterling silver"; British silver coins

and are said

are of this grade.


Silver-plating is usually done by electrolysis of the double cyanide of silver and potassium. A bar of silver forms the anode, and the object to be plated, the kathode (cf. 460). The rough " " or matt surface is given the usual lustrous finish by polishing with chalk. The double cyanide solution is made by adding to

a silver nitrate solution one of potassium cyanide


until the silver cyanide first precipitated
is

(cf.

426)

redissolved.
3.

AgN0 +KCN
3

AgCN J +KN0
KAg(CN) 2
.

KCN+AgCN
The

silver forms part of the complex negative ions, Ag(CN) 2 Mirrors are made by precipitating silver upon glass. The silver is deposited from silver nitrate solution containing am.

PHOTOGRAPHY.
monia.

423

ammonium
glass,

This solution and a suitable reducing agent, e. g., tartrate, or acetaldehyde (CH 3 CHO), are put upon the and the glass is gently heated. The bright deposit of
it

washed, dried, and covered with varnish to protect from the hydrogen sulphide, etc., of the air.
silver is

465.

Compounds
3,

.of

Silver.

Silver

nitrate,

AgN0

is

the most important

It is a white, crystalline solid,

compound of silver. made by treating silver


is
2

with dilute nitric acid.


called lunar caustic.
soluble.

Silver nitrate

sometimes
4,

Silver sulphate,
silver

Ag SO

is

also

Silver chloride,
silver iodide,

AgCl,
(cf.

Agl

bromide, AgBr, and 335), are made by adding

solutions

of

spectively, affected by light,


Silver chloride

chlorides, bromides, and iodides, reto solutions of silver salts. They are

and are used

in photography.

giving soluble salts,

and bromide " dissolve " in ammonia-water, Ag(NH3 ) 2 Cl and Ag(NH3 ) 2 Br. In these
4
.

the silver

is

silver salts,

part of the complex positive ion, Ag(NH 3 ) 2 Soluble such as the nitrate, give a precipitate with a little

ammonium
ion.

hydroxide, but

it

redissolves in an excess, owing

to the formation of soluble

compounds containing the complex

466. Photography.
Silver salts are used in

photography because they change color

and become insoluble


to light.

in certain chemicals after being exposed

When a photographic plate is exposed in a camera, no change is visible until the plate has been developed. Developng consists in treating the plate with a reducing agent, such as

424

COPPER, SILVER,

AND

GOLD.

ferrous sulphate, pyrogallic acid, hydroquinone, eikonogen, etc.

covered with the developing solution, an image appears; this is due to the precipitation of a film of silver, which produces variations of light and shade. Where the light acted strongly upon the plate, the deposit of silver is relatively heavy;

When the plate is

and where there was little action, there is little metal deposited. Just what the action of light upon the silver bromide of a plate is, is not definitely known, but it certainly makes the reduction to silver take place more easily than is the case with

The action of a developer ordinary silver bromide. illustrated by the following equation:
2

may

be

AgBr+C 6H4 (OH) +2 KOH


2

>

hydroquinone
2

Ag+2 KBr+2 H 0+C H


2

2.

quinone
In this case the reduction of the silver bromide
is

due to the

oxidation of hydroquinone to quinone. When the plate is sufficiently developed, it is rinsed Fixing. and put into a bath of sodium thiosulphate (" hypo "; cf. 268) to remove the silver salts not acted upon by light. This fixes " " the negative. The plate is called a because in it negative
light, and light objects dark. action of sodium thiosulphate upon silver salts form the soluble " mixed " salt, NaAgS 2 3

dark objects appear

The

is

to

Na

S2

+AgBr

NaBr+NaAgS,0

3.

is made by placing the film of a sensitized paper next to the negative and exposing both so that the light passes through the negative. The image may appear on the paper at " once (" printing-out papers) or may have to be developed " " (" developing papers). In either case the prints are "fixed

"

print

"

by removing the unchanged silver salt. Some papers are " toned " Toning.

in a

bath of gold chloride,

METALLURGY OF
AuCl3
, ,

GOLD.

425

or platinum chloride, PtCl 4 before fixing. Toning replaces part of the silver by gold or platinum. Blue prints are made on paper coated with a /erne salt (ferric

ammonium citrate) and potassium ferricyanide, 3 Fe(CN) 6 After exposure, the picture is developed and fixed by washing it in water. The result is a blue print on a white ground. The
.

process

is

used for copying plans,

etc.

Gold is found both native and com467. Gold. bined. Even native gold is not pure, however, but
metal
sand.
is obtained chiefly from Colorado and other western from Alaska, and from Australia, Siberia, and South Africa. The gold produced in the United States during 1910 was 4,657,018 fine ounces, worth $96,269,100. This was about

contains silver, and often iron, copper, etc. The is frequently found enclosed in quartz or quartz-

Gold

states,

one-fourth of the world's yield that year.

Gold-mining is of two 468. Metallurgy of Gold. kinds: (1) general placer-mining, and (2) veinmining.
In placer-mining the clay and sand containing the gold are washed with water. The lighter particles are thus removed; while the gold and other heavy metals remain. Gold and silver are extracted from this mixture by mercury (cf. 462; amalgamation).

Vein-mining consists in removing the gold-bearing rock from the earth and crushing it in stamp mills. The lighter materials are then washed away, and the gold is collected with mercury, as in placer-mining. Hydraulic-mining is a form of placermining done on a large scale with powerful streams of water.

426

COPPER, SILVER,

AND

GOLD.

Instead of mercury, chlorine and bromine are used to remove


gold from the crushed ore. They form the soluble gold chloride, AuCl 3 or bromide, AuBr 3 This is extracted with water, and the
.

gold

is

precipitated

by means

of charcoal or ferrous sulphate

(cf.

469).

The Cyanide Process depends upon the fact that gold is converted into the soluble double cyanide, KCN. AuCN, by a The gold is separated from solution of the alkali cyanides.
the cyanide solution by electrolysis or by means of zinc.

469. Purification of Gold. --The gold obtained by the processes described above is not pure. It can be

separated from silver by adding aqua regia, which


reacts with the gold.

The

solution

is

evaporated to

remove nitric acid, the residue is dissolved in water, and the gold is precipitated by ferrous sulphate or some other reducing agent.
3

FeS0 4 +AuCl 3

Fe 2 (S0 4 )3+FeCl 3 +Au.

462, end) gold


is

In the treatment of silver and gold with sulphuric acid (cf. is left in the kettle as a brown, spongy mass. This

washed, dried, and melted in a crucible with charcoal and

sodium carbonate.
is

The

poured into a mold, and leaves

resulting product, chemically pure gold, it as a gold brick.

mon metal

Gold is the only coma good conductor, and the most ductile and malleable substance known.
is

470. Properties and Uses. that is yellow. It

Its specific gravity is 19.3,

and

its

melting tempera-

ture 1060

C.

Gold unites directly with


not with oxygen.

Aqua

and bromine, but reacts with gold, formregia


chlorine

EXERCISES.
ing auric chloride, AuCl 3 (cf. 466; the common acids do not affect it.
Gold
is

427
"

toning "); but

by

alloying

the standard of coinage of most nations. It is hardened it with copper (10% in the United States). For

jewelry the proportion of gold varies from 40% to " carats fine" Pure gold usually given as so many
fine;

75%;
is

it is

24 carats

hence 18-carat gold

is

75%

gold and

25% alloy.

Because

of its malleability

and weak chemical

by dentists for

filling teeth.

action, gold is much used Gold-leaf is used in ornamentation.

471. Exercises.
are the atomic weights of copper, silver, and gold, Which forms the most stabk oxide (cf. 405)? The least? Which is affected most readily by the air? " 2. In the heating of copper matte in a converter/' why are
1.

What

respectively?

arsenic, lead,

form

volatile

yield in the

" poling process that could reduce copper oxide? " " dissolves in warm, concentrated hydro3. Cupric oxide chloric acid. Write the equation. When the solution is heated

"

and iron oxidized before copper? Which of these oxides? What materials might " green " wood

with copper, a white solid separates out. What is it? Write the equation for its formation. 4. From the difference in the solubilities of silver chloride,
bromide, and iodide
chloride
(cf: Appendix viii), what would happen if the and bromide were heated with a solution of potassium iodide? Give the equations. 5. How would you distinguish between the nitrates of barium, copper, cadmium, zinc, mercury (ic), and silver? 6. How would you separate the copper and silver of a silver

coin so as to recover each metal in the free state?

Write

all

the

equations.
7.

How would you

8.

separate brass into copper and zinc? Give the uses of the alloys named in this chapter.

CHAPTER XXXIV.
ALUMINUM.
472. Occurrence of

Aluminum.

num

does not occur free, it is widely distributed metal. Only oxygen and silicon Some of its most important are more abundant.
minerals are potash feldspar (KAlSi 3
vite),
is
8 ),

Although alumithe most abundant and

mica (musco-

2 KAl 3 (SiO 4 )3, and cryolite (cf. 316). Granite a mixture of quartz, feldspar, and mica. Clay results when granite and similar minerals are decomposed

(#10).
All the other elements of the

aluminum group

are

rare

(cf.

Periodic Table,

383).

473. Preparation.

Aluminum was formerly


Na
Al+3 NaCl.

pro-

duced from anhydrous aluminum chloride and sodium.


AlCl 3 +3

processes, of

This method has been superseded by electrolytic which that of Hall (1887) is perhaps the

most important.
at Niagara.
Hall's Process.

This

is

carried out on a large scale

The furnace used

in the Hall process

is

box

of boiler iron (Fig. 87), the

lined with a mixture of

bottom and sides of which are coke and tar, rammed hard. The bot428

PROPERTIES.
torn forms the
electrode, while the

429

+ electrode
rods.

consists of

forty large carbons suspended

by copper

To

bottom

begin the process, the carbons are lowered almost to the of the furnace, cryolite is put in, and the current is

turned on.

The resistance to the passage of the current produces heat enough to melt the cryolite. Pure, dry aluminum oxide, A1 2 O 3 is then mixed with the fused cryolite, and the electrolysis
,

begins.

FIG.

87.

The process is continuous, for the cryolite bath remains unchanged. The aluminum collects at the bottom, and is drawn off; the oxygen of the aluminum oxide unites with the carbons
to form carbon monoxide, which escapes.

The United

States
this

consumed over 21,600 metric tons of aluminum in 1910; was probably over two-thirds of the world's output. The aluminum oxide used is obtained from beauxite
bauxite), A1 2
3.

(or

H 0.
2

iron, silicon, etc.;

natural mineral has impurities, e. g., these are removed at present by fusing the
metallic aluminum.

The

beauxite with a

little

Aluminum is a white, lustrous 474. Properties. metal. Its specific gravity (2.6) is very low compared with that of other common metals, zinc being 7.1 and

430
iron 7.8 times as

ALUMINUM.

heavy as water. It melts at about 660 C. and vaporizes at the temperature of the Aluminum is a good conductor, is electric furnace. ductile and malleable, and has the tensile strength
of cast-iron.

Commercial aluminum
to

is

95%

to

99.6%
oxide,

pure.

At white heat aluminum burns


A1 2 O 3
.

aluminum

Hydrochloric acid readily reacts with the

metal, forming
2

aluminum

chloride.
>

Al+6 HC1

2 AlCl 3 +3

2.

Nitric acid
it

and dilute sulphuric acid do not act upon


reacts with solutions of salt

ordinarily.

Aluminum
chlorides
also,

and other

It reacts, if a little free acid is present. with the hydroxides of sodium and potassium, forming aluminates and hydrogen.
6

NaOH+2

Al

Na A10 3 +3
3

2.

Aluminum

unites directly with the halogens,

and with

carbon, silicon, nitrogen, etc.


It is probable that more aluminum 475. Uses. used in the manufacture of iron and steel than for

is

any other one purpose. The aluminum removes any oxygen the iron may have in combination, and thus increases the fluidity of cast-iron and steel.

The next important use is as a conductor of elecThe Northwestern Elevated Railroad of tricity. Chicago is using twenty miles of If -inch aluminum

ALUMINUM OXIDE AND HYDROXIDE.


cables, weighing 150,000 pounds, to transmit power to its trolley cars.

431
motive

Aluminum powder
metals,
e. g.,

is

chromic oxide, Cr 2

used to reduce the oxides of many in thermite (cf. 3 308), and


,

for flash-lights.

large part of the

aluminum produced

is

used

for kitchen utensils, scientific instruments, etc.; the aluminum alloys also require much of the metal. The alloys with copper

were described in
to

458.

The

alloy

magnalium contains 75%


It is light,

90% aluminum and

the remainder magnesium.

hard, and takes a high polish.

AlumiA1 2 O 3 occurs in the form of ruby, sapphire, and corundum. Emery, an impure form of corundum, is very hard, and is used for grinding and polishing.
476.

Aluminum Oxide and Hydroxide.


,

num oxide,

Alundum

is

an

artificial

corundum made by melting

bauxite in the electric furnace.

Aluminum
2

oxide

may

be

made by

heating the hydroxide.


Al 2
3

2 A1(OH) 8

+3 H 0.
3,

Aluminum hydroxide, A1(OH) may be precipiby adding ammonium hydroxide to the solution of an aluminum salt, e. g., aluminum chloride. Alumitated

hydroxide reacts with both acids and alkalies (except ammonium hydroxide); with acids it gives aluminum salts, and with alkalies, aluminates It is, therefore, a base toward strong 474). (cf. 363 and acids and an acid toward strong bases (cf.
368).
(1)

num

(2)

Al(OH)s+3 HC1 H3A10 3 +3 NaOH

AlCls+3

H 0. N a3A10 +3 H 0.
2 3
2

432
Many

ALUMINUM.
aluminates are derived from the meta form,

HA10 2

H 0+HA10
2

2.

477. Uses of Aluminum Hydroxide. As stated in 69 (q.v.), aluminum hydroxide has the power of entangling finely suspended clay and the germs clinging to it, The and is, therefore, used to purify water by coagulation. " " be and 284 of water hardness the 435) may (cf. temporary 478) sufficiently abundant to produce the precipitate (cf.
;

if

not, lime
(1) (2)

is

used.
2

3
[2

Ca(HC0 3 )2+Al
Al(HC0 3 ) 3

(SO 4 )3

]+6 HOH

[2

A1(HC0 3 ) 3 ]+
1

CaS0 4
2

2 A1(OH) 3

+6 H C0

3 T

Just as precipitated aluminum hydroxide takes clay particles, so it removes many coloring matters from solution. The aluminum hydroxide and coloring matter

Mordants.

up suspended

form a lake. The aluminum hydroxide acts in the same way when " it is deposited in the fibers of cloth, and thus serves to "fix so hold When color. used, dyes in fabrics that do not readily " " to bite the hydroxide is called a mordant, from the Latin
:

The aluminum hydroxide is precipitated in the cloth fibers by soaking the cloth in aluminum
the mordant
bites into

"

"

the fabric.

and then hydrolyzing the salts with the cloth, first, in the salts, and then in by soaking ammonia water. Salts of tin, chromium, iron, and copper may be used instead of aluminum salts, for all give gelatinous presalts,

such as the

acetate,

steam, or

cipitates either

when hydrolyzed,

or

when

treated with ammonia.

In making calico, the pattern is printed with a mordant, and the cloth is then exposed to a dye which combines with the mordant, but not with the cloth. The un-

Tannic acid

is

also used.

combined dye is washed out. Different parts of the pattern may be printed with different mordants; thus a number of colors

may

result

from the same dye.

ALUMINUM
Dyes. The union
out a mordant,
is

SALTS.

433

of fabric with dye-stuff, either with or with-

partly chemical and partly physical.

The

different characters of the fibers of cotton, linen, wool, and silk bring about physical differences in their dyeing. The chemical

differences are

more important;

for cotton

and linen are

chiefly

cellulose, which does not act readily with other compounds, while wool and silk contain nitrogen compounds, which are much more active. Besides insoluble, colored substances, which enter

the fibers of the cloth mechanically, dyes are usually divided


into
1.

two classes:
Direct, or substantive, dyes.

These unite directly with the

compounds. Direct dyes act far more generally with wool and silk than with cotton and linen. 2. Mordant, or adjective, dyes. These require either an acid,
fiber to

form

stable, insoluble

like tannic acid, or

a substance weakly acid or basic, like the

other mordants named, to unite them to the fiber. Thus the fiber, the mordant, and the dye react essentially like acids and
bases, producing

complex

salts,

which are the dyed

fabrics.

478.

Aluminum
is
.

Salts.

Aluminum

chloride,

A1C1 3

soluble in water, and crystallizes with crys, but it is so much hydrotal-water (A1C1 3 6 2 0)

lyzed that when the water is expelled hydrochloric acid escapes, and aluminum hydroxide remains.
AlCl3 +3

Al(OH) 3 +3 HC1.
is

The anhydrous

chloride

made by

letting

dry

hydrochloric acid gas act upon hot It is a hygroscopic, white powder.

aluminum

filings.

Alums. Aluminum sulphate, A1 2 (S0 4 )3, forms double salts with the sulphates of univalent metals, e. g., with potassium these double sulphates are called alums. The 2 S0 4 sulphate,

434
alums
crystallize
is

ALUMINUM.

with twenty-four molecules of crystal water. silver-alum is Ag2 S04 , 4 A1 2 (S0 4 ) 3 24 2 0; Other trivalent elements may replace alumiA1 2 (S0 4 )3, 24 2 0. num. Thus Na 2S04 Fe2 (S04 ) 3 24 2 would be sodium ironPotash-alum

K S0
2

Chrome-alum is K 2 S0 4 Cr 2 (S04 ) 3 24 H 2 0. Aluminum Carbonate and Sulphide. The electro-positive properties of aluminum are so weak that even its salts with strong acids, e. g., the chloride and sulphate, are readily hydrolyzed. Its salts with weak acids cannot exist in the presence of water, being completely decomposed into the hydroxide and the free
alum.
,
,

acid.

When

the acid

is volatile, it

of course escapes.
salts

This

is

the

case with the carbonate.

When aluminum

are treated

with the solution of a carbonate, the products are aluminum hydroxide and carbonic acid. Hence carbon dioxide escapes.
(1)
(2)

2 A1C1,

+3 Na C0
2

A1 2 (C0 3 ) 3
2

+6

NaCl.
2

Al 2 (C0 3 ) 3 +6

Al(OH) 3 +3

H C0

3.

With the sulphide the


(1)
(2)

result

is

similar.

2 AlCl 3 +3

(NH4 )
2

A1 2S3

+6 NH C1.
4

A1 2 S 3

+6 H

2 Al(OH) 3 +3

H S.
2

479. Porcelain, Stoneware, Etc.

Aluminum silicate, Al 2 (Si0 3 ) 3 is essentially the substance from which porcelain, etc., are made. In a pure form it is kaolin; in an impure form, clay (cf. 393). Porcelain and china are made by mixing white kaolin and quartz with more fusible substances, such as feldspar, shaping the plastic mixture into form, and "firing" it in a pottery kiln. The more fusible portion (the feldspar) melts, and cements the whole together. The first heating is at a relatively low temperature. The article is then covered with the a mixture of powdered feldspar and material of the glaze,
,

EXERCISES.
quartz, Porcelain

435

fired for several days at a high temperature. hard and translucent, and withstands the action of heat and chemicals better than glass, hence it is used for many
is

and

purposes in chemical laboratories. Stoneware is opaque, for it has not been heated enough to make the feldspar penetrate the kaolin as much as in porcelain.

Earthenware
but not fused.

is

It

made from common clay, hardened by heat, is glazed by putting common salt into the

furnace at the time of heating. This forms a covering of sodium aluminum silicate over the porous surface. Bricks, tiling, jugs,
terra-cotta etc., are examples.

Ultramarine is a blue coloring material, made by melting together kaolin, sodium carbonate, and sulphur. This substance was once very valuable, but thousands of tons of it are now

made every

j^ear.

480. Exercises.
1.

(a)

Write the equation for the following reactions: Aluminum and magnetic iron oxide, heated. (6) Aluminum chloride and excess of barium hydroxide

solution.
(c)

(d)
(e)

Decomposition of aluminum sulphate by heat. Formation of potash-alum.


Hydrolysis of aluminum acetate. Fusion of aluminum oxide with excess of sodium carbonate.

(/)

2.

What
and

are the formulas of


nitride?

carbide,

aluminum phosphate, nitrate, Of calcium metaluminate? Of ammonianext to aluminum in


its

alum?
3.

What

element

is

abundance?

Why is it so much more generally used? 4. How could you distinguish a solution
num
salt

containing an alumi-

from one containing a calcium

salt?

zinc salt?

CHAPTER XXXV.
IRON, NICKEL,

AND COBALT.
Iron
is

481. Occurrence of Iron.

one of the

most widely distributed metals, and, next to alumiIt is found in 9). num, the most abundant (cf.
the
soil,

in natural waters,

in the chlorophyll of

plants,

and

in the haemoglobin of the blood.

Some

reaches the earth in meteorites, and the spectroscope shows its presence in the sun and stars.
principal ores of iron are haematite (Fe2 (Fe 3 O 4 ), brown iron ore [Fe 2 O 3 magnetite

The

3 ),

Fe(OH) 3 ], and siderite, or spathic iron (FeCO 3 ). Iron pyrites, FeS 2 is used for its sulphur (cf. 252).
,

482. Metallurgy of iron is carried out on


is

Iron.

--The

production

of

an enormous

scale, since iron

the most useful metal. In 1910 the world's production of pig-iron was 64,860,260 metric tons. The United States produced 27,303,567 long tons.

The

become oxides; hence they by heating them with carbon (coal or 316 and 434). coke) and a, flux (limestone; cf. The limestone combines with the silica and aluminum oxide of the ore and coal, and forms slag, a glassy mixture of calcium and aluminum silicates.
ores are oxides, or

are reduced

436

METALLURGY OF
The reduction
furnaces.
Blast-Furnace.

IRON.

437

of iron ore is carried out in blast-

ture about 100 feet high.

blast-furnace (Figs. 88 and 89) is a strucThe inner walls consist of fire-brick

surrounded by brick.
is

made

of sheet-iron.

The outside The furnace

is

ore,

charged through the top with coke, " and limestone. A double bell"

(AB) permits new charges to be introduced without allowing gases to


escape through the top. A blast of hot air is forced into the furnace

through pipes, called tuyeres (T,T), near the bottom. The walls of the furnace just above the tuyeres are kept cool by a series of water pipes

(W, W). The furnace gases escape " " downcomers (C, C) through the " under the bell." The iron collects
crucible," form) in the at the bottom of the furnace, and
(in liquid

"

FIG.

88.

above
off

the slag. through the


it
is

The

iron

is

drawn
every four to
iron
is

tap-hole
(S).

(I)

six

hours; the

slag

run

off

through

The

run into molds, form-

ing the bars called "pigs" (whence the name pig-iron), or it is " converters " (cf. 487), or transferred, while still molten, to
furnaces, iron
is

and made into

steel.

In modern mills the melted

poured directly into steel molds. These are brought mechanically under the ladle, chilled in water, and emptied " into a. nearby car. Such a device is known as a pig-machine."

The operations of the blast-furnace require careful attention. Ores must be analyzed, the composition of flux and reducing agent, and their amounts, must be determined, and the temperature regulated.

When

once started, blast-furnaces con-

FIG.

89.

A BLAST

FURNACE WITH

ITS

"STOVES
438

"

AND CHARGING "SKIP."

COMMERCIAL
tinue
"
in blast

IRON.

439

"

for

months.

The

largest ones produce 500 tons,

or more, of pig-iron a day. Cast iron is a form of pig-iron. The chemical reactions of the blast-furnace are as follows:

The oxygen of the air-blast first unites _ form carbon dioxide; but this is reduced higher up to carbon monoxide (cf. 286). monoxide comes in contact with all parts of
it.

with the carbon to by the hot carbon

The gaseous carbon the ore, and reduces


.

FeaQs+3

CO 7

Fe+3 C0 2

The
is

reaction

is it

monoxide drives

forward

reversible, but the large excess of carbon (cf. 243). Some of the silica present
Silicon, sulphur,

reduced to silicon.

phosphorus, carbon, and


are, therefore,

manganese are taken up by the


in pig-iron.
is

iron,

and

present

The waste gas that

essentially producer-gas (cf. carbon monoxide. It is used to produce steam for the air-blast " " stoves (cf. Fig. 89) to heat the air engines, or burned in
itself,

escapes through the downcomers 300), and contains about 25%

or cleaned

and used

in gas engines for generating power.


calcite stone, is

Blast-furnace slag,
to

when burdened with a


(cf
.

used

make Portland cement

437)

483. Commercial Iron.

--The

various grades of

commercial iron are


other elements.

alloys of iron with carbon and The carbon may be in combined

6.6% carbon;
will

form, as a part of iron carbide (Fe 3 C), which has or it may be simply mixed with the
(cf.

iron, as graphite

272).

Any

graphite present
is

be

left

as

an insoluble residue when the iron

dissolved in dilute nitric acid of sp. gr. 1.12; but if the carbon is present as carbide, it will be partly
dissolved
(cf.

and partly given off as hydrocarbons 525). Hydrocarbons are always present in

440

IRON, NICKEL,

AND

COBALT.
(cf.
.

49) Iron carbide is very hard, and imparts hardness to The three chief subdivisions of iron containing it. commercial iron are cast iron, wrought iron, and
steel.

hydrogen made from acids and iron

Cast iron contains from 1.5% 484. Cast Iron. besides to silicon, sulphur, phosphorus, carbon, manganese, etc. (cf. 482). It is the lowest-melting

4%

form of iron (1050 to 1250


forged, or tempered.

C.).

It

cannot be welded,

Two
is

chilled) cast iron.

varieties are distinguished: gray cast iron and white (or If the iron drawn off from the blast-furnace

allowed to cool slowly, most of the iron carbide breaks up, and
is

the carbon

present chiefly as graphite.

Fe 3 C

>

Fe+C.

point,

Hence the and is


it

cast iron
easily

is gray. Gray cast iron has a low melting worked with tools. It is made into castings

by pouring

while melted into sand molds.


cooled very rapidly, the reaction

When the blast-furnace iron is

shown above has not time for its completion, and the cast iron White cast iron is is white from the presence of much carbide. very hard and brittle, and hence is not used for castings that are to be machined It is used for making wrought iron and steel, and for hard castings. Spiegeleisen and ferro-manganese are cast iron rich in manganese and carbon. They are used to add definite amounts of
these elements to wrought iron, thus

making

steel

486).

485.

Wrought

Iron.

If

the carbon and silicon

of cast iron are nearly all

removed, the iron becomes and and malleable, tough requires about 1600 C.

STEEL.
to melt
it.

441

iron can be magnetized temcan also be porarily. forged and welded, but not cast or tempered. It has usually 0.06%, or less, of

Wrought

It

carbon.

may be defined as the product of the " PudThis dling process. process consists in heating pig-iron with ferric oxide (iron ore) in an air current upon the hearth of a reverWrought
"
iron

The mixture melts, and the 462) beratory furnace (Fig. 86, impurities of the cast iron are oxidized. The carbon escapes as carbon monoxide, while the oxidized silicon, phosphorus, etc.,
.

unite with some, of the iron to form a slag. The mass is stirred, or "puddled," to permit the air to get at the impurities. As the proportion of the higher melting, pure iron becomes greater, the puddled mass acquires a pasty consistency, and finally it

made into a ball, or " bloom." This is taken from the furnace and hammered with a steam hammer, or rolled, to remove
can be

most of the slag. While the structure of cast iron is crystalline, that of wrought iron is fibrous. Between 900 and 1000 C. wrought iron becomes plastic, and while in this condition can be hammered, drawn out into wire, and rolled into sheets or bars. Wrought iron can also be welded, that is, pieces can be joined by hammering. The film of oxide that covers the parts to be welded is

removed by sprinkling them with borax

399) or with (cf. sand, which convert the oxide into iron borate, or silicate, and permit iron actually to touch iron.

Malleable Iron. When iron castings are covered with iron and heated, the oxygen of the ore combines with much of the carbon of the cast iron, and the castings are converted into a malleable form. Malleable iron is thus a cheap wrought iron.
ore,

486. Steel.

Steel

is

a form of iron containing


all

under 2.2% carbon (practically

of

which

is

in

442

IRON, NICKEL,

AND

COBALT.

and comparatively small the combined state) amounts of sulphur and phosphorus. It contains more carbon and silicon than wrought iron, and less
than cast carbon is mild steel.
iron.

Steel

containing about

0.2%

of

like wrought iron, and is called " Steel used for buildings (" structural while steel) contains more carbon (0.2% to 0.8%) ; The melting tool steel hag about 0.8% to 1.5%.
is

much

point of steel

between the melting points of cast

wrought iron (about 1475 C.). Steel combines the advantages of both cast iron and wrought iron; for it may be forged, welded, " and cast. It has, besides, the power of being temof

and

pered

"

to different degrees of hardness

489).

(1)
(2)

Steel may be made 487. Manufacture of Steel. by removing part of the carbon from cast iron;

to wrought iron; and (3) by cast iron and either wrought iron melting together " " or blown iron. Method (1) is rarely used now; method (2) is applied in the crucible and cementa-

by adding carbon

method (3) is the Open Hearth (Siemens-Martin) processes. To these must be added the new process of making " Electric " steel, in
tion processes of making steel; basis of the Bessemer and the

which the
A.

electric

furnace

is

employed.
"

The Bessemer Process.

The Bessemer
a
converter

essentially in reducing pig-iron in


iron,

process consists " " blown " to

and then adding enough high-manganese cast iron

MANUFACTURE OF
"

STEEL.

443

" - to bring the proportion of carbon up to the spiegeleisen amount wanted. The converter (Fig. 90) is a pear-shaped furnace, 20 feet or more in height, and mounted upon trunnions (S) so that it can

be inverted.

Molten pig-iron
(

is

taken directly from the blast-

furnace to the converter

blast of air enters through " " one trunnion, and is forced up through tuyeres at the bottom This oxidizes the silicon, manganese, and carbon of the (T).

482),

and a

pig-iron.

The heat pro-

duced by this oxidation


keeps the iron melted. The manganese of the " reduces

spiegeleisen" the iron oxide formed " during the blow," and is thereby converted
into

-Air

manganese
separates

oxide,

which

with

the slag.

When
ing
is

silica linFIG.
90.

used in the conthe process


is

verter,

called the acid

Bessemer process.

The

acid process cannot lower

the phosphorus and sulphur content of the pig-iron used. All Bessemer plants in this country are acid. In Europe the ores

permit the use of the basic Bessemer process. In this process the converter lining is basic (lime and magnesia), and a pig-iron The reason for of very high phosphorus content is required. this is that the oxidation of the phosphorus furnishes the heat
required to keep the metal molten, just as the oxidation of silicon does in the acid process. The slag made in the basic process
contains phosphates.
("
It
is

ground up and sold as


10 to 20 tons of steel at a

fertilizer

Thomas

slag ";

cf.

358).

A converter usually makes

"

blow."

444

IRON, NICKEL,

AND

COBALT.

The time taken is fifteen to twenty minutes. Bessemer steel contains about 0.35% carbon. It is used for rails, axles, cannon,
wire, tin-plate,

and structural purposes.

Process. .In the Open Hearth process pigiron, wrought iron, or steel scrap is heated with iron oxide (ore) in an open hearth (reverberatory) furnace (cf. Fig. 86,

B.

Open Hearth

462).

An

oxidizing gas-flame

is

used.

The furnace
air are

consists

essentially of a hearth to hold the charge,

and a roof to
is

direct

the gas-flame

down upon

it.

The

gas and

brought to-

very high. brought about by passing each of the two gases through fire-brick heated by the products of com-

gether hot, so that the temperature of the flame

The preliminary heating

is

bustion as they leave the furnace. By the reversal of the direction of the incoming and outgoing furnace gases by means of
suitable valves the bricks cooled by the entering gas and air are heated again by the outgoing products of combustion. If the pig-iron used contains much phosphorus, a lining of lime and

magnesia

may

select material is available the acid process

be used (basic open hearth furnace); but if may be used. Acid


for first-class castings.

open hearth

steel is preferable

Samples are taken from the furnace at intervals to determine when the per cent of carbon has been lowered sufficiently. The charge is usually from 20 to 100 tons; the process takes from
eight to eleven hours. Steel made in this way is very tough and elastic, and suitable for the finest structural work, such as
bridges,

and for machinery bearings, boiler-plate, large guns, etc. Because of the excellent quality of open hearth steel the amount of it produced has gained rapidly upon Bessemer steel, until

(1912) the two are about equal in this country. C. Crucible and Cementation Steel. The Crucible process consists in heating a very pure wrought iron and pure cast iron together in a graphite crucible (cf. 272). The fact that crucible
steel is
air,

now

made
it

in a reducing atmosphere,

makes

remarkably

free

and in the absence of from oxides and occluded gases


.

TEMPERING OF STEEL.

445

Because it is cheaper, it is replacing cementation steel. In the cementation process wrought iron is packed in charcoal, and heated to redness for several days. As in the crucible process, carbon is gradually absorbed by the metal.

488. Steel Alloys.


Manganese, chromium, nickel, vanadium, tungsten, molybdenum, and silicon are mixed with steel for special purThus poses, as for imparting great hardness or toughness. nickel steel is used for armor plate, and chrome steel for automobile bearings. Tungsten steel is self-hardening ; tools made from To make certain special steels, in it require no tempering. which great homogeneity and freedom from oxides and slags are

The titanium desired, ferro-titanium (10% to 15% Ti) is added. unites readily with nitrogen and with oxygen, giving Ti 3 4 and Ti0 2 and adds fluidity to the slag.

When steel conTempering of Steel. taining above 0.5% carbon is heated to cherry redness (above 670 C.), and then cooled quickly in water or oil, it becomes hard as glass, and can be
489.

given a sharp edge, such as is required for cutting If the hardened steel is reheated, and then tools. allowed to cool slowly, it becomes soft. This
process
If,

is

called annealing, or

"

however, the hardened

steel is

drawing the temper." heated up slowly


it is

until a film of oxides of a particular color appears

upon the surface


into water or

of the steel,
it will

and

then plunged

oil,

hardness.
films

This

is

retain a definite degree of The colored called tempering.

are

generally

removed from the tempered

446
article

IRON, NICKEL,

AND

COBALT.

They correspond roughly to grinding. certain degrees of temperature, as is shown in the


by
Temperature.
610 C.
530
Color.
Blue-black.
Blue.

following table:

Use
Saws.

of Steel.

-570.

Watch
Shears.

Springs.

520. 490 -510. 470. 430 -450.

Purple.

Table Knives.
Pocket Knives.
Razors.

Brown.
Bright Yellow. Pale Yellow.

490. Causes of the Behavior of Iron

and

Steel. -

Two

things

behavior of

must be kept iron and steel


:

in

mind

in studying the

(1) Pure iron exists in several allotropic forms, and only one of these can dissolve carbon (as carbide) in any considerable amount. (2) Iron carbide imparts hardness to cast iron and steel, but decomposes below 670 C.

Fe 3 C

",

Fe+C.

The forms

of iron

and

their properties are:

A.

Stable below 765 C.

PROPERTIES OF IRON.

447

up into pure (wrought) iron and graphite. But sudden cooling does not allow time for these changes. Chilled cast iron ( 484)
is

solid solution of

Fe3 C

in iron of
it

form C.

Hard

steel rep-

resents a similar condition, but


tically

has

less carbide,

and prac-

no sulphur and phosphorus. When the steel is gradually re-heated (tempered), there is a partial change of iron C into A, and a partial decomposition of the iron carbide; hence the steel
is

softened.

because of their

The metals present in steel alloys own peculiar properties, but

are used, not only


also because they

prevent, or retard, the change of iron C into A. Since the properties of an iron alloy depend both upon the proportions of pure

and graphite present, and also upon their condition in the mixture, the best way to study iron is to polish a section of it, to etch the polished face with an acid, and then
iron, iron carbide,

to examine

it

carefully with the microscope.

The

constituents

and

their condition can thus be determined.

Pure iron is rare; it 491. Properties of Iron. melts at about 1800 C. The purest commercial form is wrought iron; this is a fairly good conductor.
Soft,
i.

e.,

wrought, iron

may

soon loses the magnetism; steel becomes a permanent magnet.

is

be magnetized temporarily, but not so easily magnetized, but

At red heat
3

iron decomposes water vapor.

Fe+4

HO"
2
f

Fe 3

+4 H

2.

burned in oxygen the same oxide reIn dry air iron does not change, but in the presence of moisture and carbon dioxide it
iron
is

When

sults

(cf.

24).

rusts.

a mixture of ferric oxide (Fe 2 3 ) and ferric hydroxide, Fe(OH) 3 Iron reacts easily Iron rust
is
.

448

IRON, NICKEL,

AND

COBALT.
salts,

with dilute acids, forming ferrous


iron
is

bivalent.

which These are readily oxidized, even


in

by the oxygen of the air, to ferric salts, containing Ferric salts are reduced trivalent iron (cf. 181).
sulphide, stannous chloride, and nascent hydrogen to the ferrous state. Solutions containing ferrous ions are pale green; those of ferric ions

by hydrogen

are yellow or light brown.

492. Oxides
be

and Hydroxides
is

of Iron.

Ferrous oxide (FeO)

made by reducing
Ferric oxide, Fe 2
3,

ferric

not easily prepared or kept. It may oxide with hydrogen at 300 C.,

but on exposure to
It

air it is oxidized at once.


is

found in enormous masses (haematite).


ferric hydroxide or ferrous sulphate.

may

be made by heating
2

Fe(OH) 3

>

Fe 2

+3 H 0.
2

Ferrous-ferric oxide, Fe3 4 is called the magnetic ox" It is sometimes found as of iron; it occurs as magnetite. ide
,

"

a natural magnet. Iron may be kept from rusting by exposing it while red hot to steam; the resulting layer of the black oxide, Fe 3 4 protects the remainder of the metal. Iron
lodestone,
,

so coated

is

Russia

iron.

Ferrous hydroxide, Fe(OH)2, is formed when an alkali in solution is added to the solution of a ferrous salt. It is usually green, but soon becomes brown where air is in contact with it. In the absence of air it is white.
or

hydroxide, Fe(OH) 3 is made by adding an alkali to the solution of a ferric salt. It forms a red-brown precipitate. flaky,
Ferric
,

ammonia water

IRON CHLORIDES.

449

493. Iron Sulphides. Ferrous sulphide, FeS (cf. 250), is a black solid made by heating a mixture of sulphur and iron, and by adding an alkali
sulphide to a ferrous salt solution.

K S+FeCl
2

FeS+2 KC1.

Hydrogen sulphide
from a ferrous
ferrous state. ferrous ions,
ferric salts.

salt (cf.

precipitates only a trace of ferrous sulphide 255), and reduces a ferric salt to the

Ammonium
and thus

sulphide also reduces ferric ions to

precipitates

FeS from both

ferrous

and

"

fool's gold."

Iron pyrites (FeS 2 ) has the color of brass, and For its behavior when heated, see 252.

is

called

494. Iron
is

chloride, FeCl2 , over hot iron. chloride passing hydrogen solution of it results when iron is treated with the

Chlorides.

Ferrous

made by

Like all ferrous compounds it is oxidized The anhydrous salt easily to the ferric condition.
acid.
is

white.
In the presence of hydrochloric acid the
air oxidizes it to

ferric chloride.

4 FeCl 2 +4
If
salt,

HC1+0

4 FeCl 3 +2
is

H 0.
2

no acid is present, part of the iron and part to ferric hydroxide (rust)
.

oxidized to ferric

12

FeCl 2 +3

+6 H

8 FeCl 3 +4 Fe(OH) 3

Ferric chloride, FeCl 3 is formed in solution passing chlorine into ferrous chloride solution, or
,

by by

treating iron with aqua regia,


peatedly

with

hydrochloric

acid.

and evaporating reThe anhydrous

450
salt is

IRON, NICKEL,

AND

COBALT.

made by

passing chlorine over red-hot iron.

It looks like maple-sugar.

495. Iron
sulphate,

Sulphates.
,

FeS0 4

results

when
.

ferrous iron reacts with dilute

solution

of

The crystals sulphuric acid. " " or are FeS0 4 7 copperas

known

as green vitriol

H 0.
2

Green

vitriol is

used in making inks, in dyeing, and as a deodorizer. Common writing ink is ferric tannate (cf. 546),

suspended in water by means of dissolved


or dextrin.
It is

gum

arabic
of

made by

treating an extract

The resulting fernut-galls with ferrous sulphate. rous tannate is oxidized by the air. The double salt,
ferrous

H 0,
2

is

ammonium sulphate, (NH4 ) 2 S0 4 FeS0 4 6 much less easily oxidized than ferrous sul.

phate alone.
Ferric sulphate, Fe 2 (S0 4 ) 3 is made, in solution, by oxidizing ferrous sulphate with nitric acid in the
,

presence of sulphuric acid.


496. Ferro- and Ferri-cyanides. Potassium ferrocyanide, K4Fe(CN) 6
prussiate
(i. e.,

is

called
It is

"

yellow

cyanide,

cf.

290) of potassium."

a yellow,

crystalline solid

made by

heating together potash, iron, and

animal matter, such as hoofs and horns. With a ferric salt it With a ferrous salt it gives Prussian blue, Fe 4 [Fe(CN) 6 3 2 FeFe(CN) 6 Potassium ferngives a white precipitate of
]
.

cyanide, K Fe(CN)
3

oxidizing the ferrocyanide with chlorine. It is a red, crystalline solid. With a ferrous salt it gives Turnbull's blue, Fe 3 [Fe(CN) 6 3 2 ; with a ferric salt, a
6,

is

made by

brown solution of Fe(CN) 3

NICKEL.
The
ferrous

451

divided formula,
in

potassium ferrocyanide
.

Fe(CN) 2 4 KCN, shows that iron is In (ferro- means ferrous).


. ,

the ferricyanide, Fe(CN) 3 3 KCN, iron is in the ferric condition. Ferric thiocyanate, Fe(SCN) 3 is present in the blood-red
solution produced
(i. e.,

SCN

ions;
is

by adding potassium thiocyanate, KSCN 426), to a ferric salt. The corresponding cf.

ferrous salt

colorless.

Blue-print paper contains a ferric salt and potassium ferri466). Exposure to light reduces the ferric salt cyanide (cf.
to the ferrous state,

and TurnbulTs blue

results.

Washing

removes the unchanged materials. Both Prussian blue and Turnbull's blue are soluble in alkalies, because decomposed into iron hydroxides and ferro- or ferricyanides.

497. Nickel. meteorites.

Nickel
silicate

is

found
nickel

with

iron

in

of

and magnesium,

Caledonia, is its chief ore. garnierite, found in and nickel The is Niccolite NiAs, glance, NiAsS.

New

metal

may

be obtained by reducing

its

oxide with
308)
.

hydrogen, carbon, or

aluminum

(cf.

Like

It is used to plate other iron, nickel is magnetic. from the atmosphere; also them to metals protect to make alloys, such as German silver, nickel steel,

and the United States

five-cent piece.

salts,

Nickel forms nickelous oxide and hydroxide, and nickelous It also forms nickelic in which the metal is bivalent.
;

and hydroxide, Ni(OH) 3 but no nickelic salts. 3) Nickel reacts very slowly with hydrochloric and sulphuric acids, but readily with nitric acid. Nickelous oxide and hydroxide are
oxide (Ni 2
green, insoluble solids. Nickelic oxide Nickelous salts are green in solution.

and hydroxide are black.

The sulphate

crystallizes

452
as

IRON, NICKEL,
.

AND

COBALT.
.

sulphide, black. The sulphides. precipitated by dissolves in an of excess 2 Ni(CN) potassium cyanide, cyanide,
2
2

NiS0 4
is

H 0;

the chloride, as NiCl 2 6


alkali

H O.
It

The

NiS,

is

giving

K Ni(CN)
2

4.

Nickel carbonyl, Ni(CO) 4


is

is

formed when carbon monoxide

passed over finely divided nickel at the ordinary temperature. It is a colorless liquid boiling at 43 C. It is dissociated at 150

180.

Ni+4CO^=Ni(CO)
Nickel carbonyl
is

4.

to separate nickel from cobalt, which does not

its ores, and form a similar compound. Iron forms the carbonyls Fe(CO) 4 and Fe(CO) 5 In the oxidizing flame nickel compounds form a brown borax
.

used to extract nickel from

bead.

found as cobaltite, CoAsS, and smaltite, CoAs2, associated with the correspondRoasting produces the oxide, and ing nickel ores. The this is reduced with hydrogen or charcoal. metal is white, with a pinkish cast, while nickel is Like nickel and iron it is magnetic. yellowish. It reacts slowly with all acids but nitric acid.
498. Cobalt.

Cobalt

is

Cobalt forms the oxides CoO,

Co 2 0s, and Co 3

4.

The

first

corresponds to cobaltous, the second to cobaltic


salt solutions,
blue.
i. e.,

salts.

Cobaltous

Co

ions, are pink.

The
3) 2 .

chloride crystallizes as

The molecular salts are CoCl 2 6 H 2 0, the nitrate as


.

Co(N0
silicate

is

porcelain. change of the hydrated, pink cobalt salts to the anhydrous, blue " ones is the basis of sympathetic inks," which are practically
,

and the sulphate as CoS0 4 7 H 2 0. Cobalt smalt, a deep-blue pigment for coloring glass and The aluminate, Co(A10 2 ) 2 is Thenard's blue. The
6

H 0,
2

EXERCISES.
invisible

453

under the ordinary (damp) atmospheric conditions, but

become blue, and visible, when dried. Sodium hydroxide and cobaltous salts give blue basic salts, which are converted, by heating, into red Co(OH)2. The cyanide, Co(CN)2, is soluble in an excess of potassium cyanide, giving

K Co(CN)
4

6.

This corresponds to K4Fe(CN) 6


ah-,

It

is

easily oxid-

ized,

even by the

to

K Co(CN)
3

6.

cobaltous salt reacts with potassium


3

nitrite
2) 6 ,

and

acetic acid

to give a yellow precipitate of This is potassium cobaltic 3 2

K Co(N0
nitrite.

i. e.,

Co(N0

2) 3 .

KN0

Nickel forms no salts


.

Both nickel and 3 Co(N0 2 ) 6 3 Co(CN) 6 or resembling either cobalt give complex positive ions with excess of ammonia water
(c/.

ble.

The salts of these complex ions are solu459 and 465) Iron forms no such compounds. Cobalt compounds color
.

the borax and metaphosphate beads blue.

499. Exercises.
i.

(a)
(b)
(c)

Write the equations for the following reactions: Limestone and silica; limestone and aluminum oxide.
Ferric oxide

Iron carbide and hydrochloric acid. and borax; ferric oxide and sand.
Ferric chloride

(d)
(e)

Ferric sulphate

and hydrogen sulphide. and nascent hydrogen.

(/)

(g}

Hydrolysis of ferric nitrate. Ferrous sulphate, dilute sulphuric acid, and nitric acid.
Ferric salt

(h)
(i)

and ammonia water.


air.

(j)

Oxidation of ferrous hydroxide (moist) by Ferrous salt and ammonium sulphide.


Ferric salt

(k)
(/)

and ammonium sulphide (stages). Iron and aqua regia. (m) Ferrous salt and potassium ferricyanide. (n) Ferrous salt and potassium ferrocyanide.
(o)

Ferric salt

(p) Ferric salt

and potassium ferricyanide. and potassium ferrocyanide.

454

IRON, NICKEL,

AND

COBALT,

(q) Ferric salt


'

and ammonium thiocyanate.

TurnbmTs blue with caustic soda. Write the equations for the reactions by which the following are prepared from cobalt nitrate: cobalt hydroxide, oxide, and cyanide; potassium cobaltocyanide, potassium cobalti(r)

Prussian and

2.

cyanide.
3. Write the equations for the preparation of the following from nickel nitrate: nickel oxide, hydroxide, sulphate, and

sulphide; potassium nickel cyanide. 4. Give all the ways in which iron, nickel,
alike.

In what respects do they differ?


ferric,

How

and cobalt are would you distinions in

guish between ferrous, solution?

cobaltous,

and nickelous

CHAPTER XXXVI.
MANGANESE AND CHROMIUM.
Manganese occurs as the dioxpyrolusite; also as hausmannite (Mn 3 4 ) and manganese spar (MnC0 3 ). The metal is made by reducing its oxides with aluminum It is hard, brittle, steel-gray, and non308). (cf. magnetic. Manganese melts at about 1300 C., rusts in moist air, and replaces the hydrogen of the
500. Manganese. ide (Mn0 2 ), which
is

ordinary

dilute
is

acids,

giving

manganous
(cf.

salts.

Manganese
501.

used in making

steel

484).

Manganese
IV
2,

Compounds. - - The
the
VI

oxides of

manganese have

formulas
3,

Mn

4,

Mn O Mn O
last,

and
is

Mn Mn
2

IZ

O,
7.

Mn

in
2 3,

VII

All

are

solids

but the

which

a dark liquid.
manganous oxide (MnO).

The only decidedly


This
is

basic oxide

is

Mn

a green, amorphous solid, formed when the carbonate (MnCOa) is heated in absence of air. The air oxidizes it to 3 4 Manganous hydroxide, Mn(OH) 2 is precipitated as a
. ,

white

solid, insoluble in

an excess

of the strong bases;

it

has

no acid properties.

It

is

easily oxidized

2 3 hydrate of manganic oxide, salts are all manganous. When the higher oxides of
.

Mn

by the air to the dark H 20. The stable manganese


manganese

are treated with acids, they lose all the oxygen they contain in excess of that represented by the formula MnO. The excess of
455

456
oxygen
dioxide
is
is

MANGANESE AND CHROMIUM.


either given off as such, as
is

the case

when manganese

heated with concentrated sulphuric acid, or the oxygen is used in oxidizing the acid, as is the case with hydrochloric 115 and 138). acid. The resulting salts are manganous (cf.

The common manganous


solids.
.

salts

are pink,

crystalline,

soluble

Manganous sulphate crystallizes with different proporThe chloride tions of water (MnS0 4 7 2 0, 5 2 0, or 4 2 0). The carbonate is a white, insoluble solid. is MnClo. 4 2 0.

The sulphide (MnS)

is

precipitated as a light-pink solid

by

soluble metal sulphides,

but not by hydrogen sulphide (cf. The oxide Mn 3 04 is formed when the other oxides are 255). The dioxide is the most important manheated in air (cf. 22)
.

ganese compound.

It

is

used to prepare manganese, chlorine,


glass.

and oxygen, and to decolorize

It

makes

glass colorless

by

neutralizing the green color produced by the iron present in the materials used (cf. 394) Manganese dioxide is the an.

and 4 Mn0 4 2 Mn0 3 hydride of the unstable compounds These are the " ortho " and the " meta " form of manganous acid
.

(cf.

355).

Calcium manganite
2

is
4.

CaMnOs.
In the

Hausmannite

is

manganous manganite,
In the reducing flame

Mn Mn0

oxidizing flame

manganese compounds form an amethyst-colored borax bead.


it is colorless.

502.

Manganates

and Permanganates.

Man-

ganese trioxide
acid,

H MnO
2

anhydride of acid is not known in the free

3 ) is the anhydride of manganic and the heptoxide (Mn2 O 7 ) is the permanganic acid, HMn0 4 Manganic 4,
.

(MnO

K MnO
2

4,

are hydrolyzed
i.

Its salts, e. g., in solution. Manganate


state.

solutions,

e.,

Mn0

ions, are green.

Permanganic

a strong acid. It can be prepared (as a hydrate), but is unstable. Permanganate ions
acid
is

(Mn0

4)

are purple.

MANGANATES AND PERMANGANATES.

457

A manganate is formed by fusing together a manganese compound, a base (or alkali carbonate), and an oxidizing agent, such
as potassium nitrate or chlorate. used, the equations are
:

If

manganous sulphate

is

(1)
(2)

MnS0
KClOs

+K C0
2 3)

(MnC0

(3)
(4) (5)

(MnC0 )+K S0 (MnO)+C0 T KC1+3 0.


3
3 2 2
.

4.

(MnO)+20

(Mn0 3 ).
3

K C0 +Mn0
2

K Mn0 +C0
2 4

If

Mn0

is

used, equations (1)

and

(2) are

omitted.

Permanganates are formed by the oxidation of manganates. Thus ozone converts potassium manganate into the permanganate.
(1)
(2) (3)

K Mn0 +2 HOH 2 H Mn0 +0 KOH+HMn0


2

",

2 KOH+H Mn0 HMn0 +H 0+0 KMn0 +H 0.


*
2 4 2 4 2

4.

2.

The

best

way
It
is
2

and permanganic acids


anhydrides. of 3 to

to represent the relation between manganic is to consider them as hydrates of their

thus
7.

made

plain that the change


(2)

is

an oxidation

Mn0

Mn

Equation
2 3

then becomes:

(Mn0

3.

H 0)+0

Mn

7.

H 0+H 0+O
2 2

2.

Carbon dioxide also converts a manganate solution into one of permanganate; but some of the manganate is reduced to manganese dioxide to provide the necessary oxygen.
(1)

K Mn0 +6 HOH 7 H 0)].


2 4 2

KOH+3 H Mn0
2
7. 2

4 [i. e.,

(Mn0

3,

(2)
(3)

(MnO 3 HiO)
.

Mn
3

(4)

KOH+2 H C0 4 H 0. 2 KOH+2 HMn0


4
2 2

(i.

e.,

2 2

H 0+Mn0 | +2 H 0. 2 K C0 + H 0+.2 C0
2
2 2 2)

KMn0 +2 H 0.
4 2

458
If

MANGANESE AND CHROMIUM.


we omit the formulas appearing on both
"
sides of the equa-

tion, the

"

complete
4
2

equation
2

is:

K Mn0 +2 H CO*
2

K C0 +2 KMn0 +Mn0 1 + 2H O.
2 3

Other dilute acids

may be used in place of the

carbonic acid.

Potassium permanganate separates from solution Its solution is deep purple. as greenish-black prisms. When the solid is heated, it is decomposed.
2

KMnO

K Mn0 +MnO +O
2
4 2

A crude permanganate solution, made from sodium


manganate and
disinfectant.

dilute sulphuric acid,

is

used as a

by Potassium Permanganate. Potassium permanganate is used for oxidizing purposes under acid, neutral, and alkaline conditions. Oxidation in acid solution is most common. As the
503. Oxidation
is used up, the purple color disappears, because the resulting manganous salt solution is This fact makes it possible to use potascolorless.

oxygen

sium permanganate solution in volumetric analysis. To determine the amount of some reducing agent, e. g., oxalic acid, in a solution we need only find out

how much potassium permanganate solution, of known concentration, the oxalic acid can decolorize. The concentrations of solutions of formic acid,
ferrous
etc.,
salts, sulphurous acid, hydrogen peroxide, can be obtained in the same way. In acid

OXIDATION BY PERMANGANATE,
solutions 2 gram-molecular weights of give 5 gram-atomic weights of oxygen.

459

permanganate

The

following are the partial equations for the action of

acidified

permanganate with
2
4
2

oxalic acid.

(1) (2) (3) (4) (5)

(2HMn0
(Mn
(2
2 7)

KMn0 +H S0 ;i^K S0 +(2HMn0 H 0+(Mn


4
2

4 ).

4)

7 ).

(2MnO) + (50).
2

MnO)+2 H S0 H C +(5 0)
2 2

2 5
2

MnS0 +2 H 0.
4

H 0+10 C0

For the oxidation comes


:

of

FeS0 4

to

Fe 2 (S0 4 ) 3 equation

(5)

be-

10

FeS0 4 +5

H S0
2

+(5 0)

5 Fe 2 (S0 4 ) 3 +5

H 0.
2

In complete form these equations are


2

K S0 +2 MnS0 + +3 H S0 8H 0+10C0 T. K S0 +2 MnS0 + 2 KMn0 +10 FeS0 +8 H S0 8 H 0+5 Fe (S0


KMn0 +5 H C
4
2

4) 3 .

Hydrochloric reduces it; HC1

acid
is,

both liberates permanganic acid and

therefore, substituted for

H S0
2

in equations

Potassium per(1) (4), and for H 2 C 2 4 in equation (5). manganate and hydrogen peroxide reduce each other (cf. 340)

and

with liberation of oxygen.


2

KMn0 +5 H
4

+3 H S0
2

4 2

K S0 +2 MnS0 +
2

H 0+5
2

When

potassium permanganate

is

used in neutral or alkaline

solution, 2 gram-molecular weights of the gram-atomic weights of available oxygen.

permanganate give 3

460
(1) (2) (3)

MANGANESE AND CHROMIUM.


2
2 KOH+(2 HMn0 KMn0 +2 HOH 7 H 0+(Mn HMnO 2 Mn0 +(3 O). (Mn
4
4)

4 ).

(2

7 ).

7)

Chromium is a comparatively 504. Chromium. rare element, which occurs as chromite, Fe(Cr0 2 ) 2
,

i.

e.,

FeO.Cr2

3.

The metal
Cr2
3,

is

prepared by reduc(cf.

ing chromic oxide,


It
is

with aluminum

308).

It is

steel-gray, very hard, and very difficult to fuse. " " chrome-steel used in the alloy 488). (cf.

" "

Chromium
color."

"

is

from the Greek chroma, meaning

505.

Chromium Oxides and Hydroxides.


forms chromous oxide (Cr"O),
chromic
VI

Chrooxide

mium

Chro3 ). (Cr^'Os), and chromium trioxide (Cr mous salts are derived from CrO; chromic salts Chromium trioxide is chromic anfrom Cr2 3
.

hydride

(cf.

507).
is

Chromic oxide

the pigment

"

chrome-green."
,

It is

made

by dehydrating its hydroxide, Cr(OH) 3 and by heating a mixture of ammonium chloride, potassium dichromate, and sodium carbonate. The last need not appear in the equation.

K Cr
2

+2 NH

C1

KC1+N
,

+4 H 0+Cr
2

3.

Chromic hydroxide, Cr(OH) 3 is formed as a green precipitate when an alkali hydroxide, carbonate or sulphide is added to a chromic salt. It is a weak base, like aluminum hydroxide;
hence
its
(cf.

water

carbonate and sulphide are completely hydrolyzed by It is also a weak acid, and dissolves in an 478).

excess of a strong base, forming a chromite.

Chromites form

CHROMOUS AND CHROMIC SALTS.


green solutions. " "

461

They
form,

are derived from the hydroxide,


2

H Cr0
3

3,

or the

meta

HCr0
3

(cf.

355 and 501).

NaOH+H Cr0
When
the solution
is

<

NaCr0 2 +2
it is

H 0.
2

boiled,

hydrolyzed, giving a precipi-

tate of the hydroxide.

506.

Chromous and Chromic

Salts.

Chromous
,

salts are

derived from the hydroxide, Cr(OH) 2 and the oxide, CrO. These are basic, like the correspond-

ing ferrous

and manganous compounds.

Chromous

++

Chromous salts are so readily ions (Cr) are blue. oxidized to the chromic state that they are hard to
prepare.

manganous
chloride,

In this they resemble ferrous but not salts. The chief chromic salts are the
,

CrCl 3 the
2
2

sulphate,

Cr2 (S0 4 )3, and chrome-

alum,

K Cr

(S0

4 )4.

24

H 0.
2

Chromium compounds
or

give an bead.

emerald-green

borax

metaphosphate

Chromic chloride is a lavender-colored solid when anhydrous. when chlorine is passed over a mixture of chromic oxide and carbon.
It is obtained

Cr 2

+3 C+3

C1 2
is

2 CrCl 3 +3
green,

CO.
in

green crystals, CrCl 3 6


.

In solution, chromic chloride H 20.

and can be obtained

Chromic sulphate forms a

violet solution with cold water.


at
tJie
2

When

the solution

is

evaporated
.

reddish-violet crystals [Cr 2 (S0 4 ) 3

15

H 0]

ordinary temperature, separate out. If the

solution
sticky,

is

heated,

it

dark mass.

becomes green, and on evaporation gives a Chrome-alum behaves in the same way.

462

MANGANESE AND CHROMIUM.


large, octahedral, violet-colored crystals
is
(cf.
.

Chrome-alum forms
(cf.

478).

It

is

formed when potassium dichromate


.

used as
509).

an oxidizing agent in the presence of sulphuric acid Chrome-alum is used in dyeing and tanning (cf 477)

507.

Chromium

Trioxide.

Chromium

trioxide

resembles the higher oxides of manganese in being the anhydride of acids. Chromic acid is 2 CrO 4
(or
2

H O.Cr0
2

3 ),

and dichromic acid

is

H H Cr O
2

H 0.

(or

CrO 3 ).

Chromium

is
;

in the

same periodic

but while sulphuric group with sulphur (cf. 383) acid is stable, chromic acid is too unstable to be
prepared.
Its solution gives

the anhydride

when

evaporated.

This
trioxide

is
is

often called chromic acid.

Chromium

centrated sulphuric acid potassium dichromate.

formed in bright-red crystals when conis added to a saturated solution of

K Cr
2

+2 H S0
2
7)

^Z
2

KHS0 +(H Cr O
4
2

7 ).

(H 2 Cr 2
It is
it

H 0+2 Cr0

3.

breaks

a powerful oxidizing agent, owing to the ease with which down into chromic oxide and oxygen.

4
It

Cr0 3

2 Cr 2

3 -f-3

2.

sets fire

substances,

to alcohol dropped upon it, destroys organic such as paper, and oxidizes hydrochloric acid.

When it is heated, oxygen is set free.

Chromates and Bichromates. Chromium compounds are made from the chromates or dichromates (cf. 504 to 507). Potassium chromate is
508.

CHRO MATES AND BICHROMATES.

463
,

made from
it

chromite,

Fe(Cr02 ) 2

or

FeO.Cr2 O 3 by

with potassium carbonate and quicklime roasting in the oxidizing flame of a reverberatory furnace On a small scale, chromite is heated 462) (cf.
.

with a mixture of potassium nitrate and carbonate.


The methods given show
that

we
it

convert a chromium comin the presence of a base.

pound to a chromate by oxidizing For Cr 2 (S0 4 ) 3 the equations are:


(1)

Cr2 (S0 4 ) 3 +3
[Cr2
3]

K C0
2
3]

3 3

[Cr 2 (C0 3 ) 3 ]+3

K S0
2

4.

(2) [Cr 2 (C0 3 ) 3 ]

[Cr 2

]+3C0
].

T.

(3)
(4)

+ [30] K C0 +[2 Cr0


2
3

[2Cr0 8
2

K Cr0 +2 C0
2

For the preparation


(1)

of a

chromate from chromite, equations

and

(2) are

omitted.

Oxidation of a chromic compound to a chromate

may

also

take place in solution, as by adding chlorine to an alkali chromite, i. e., to chromic hydroxide dissolved in an excess of alkali.
(1)

Cr 2 (S0 4 ) 3 +6
2
]

(2)

(3)
(4)

Cr(OH) 3 +2 [2 Cr(OH) 3
[Cr 2
3

NaOH NaOH

3
7
3

Na S04 +[2 Cr(OH) 3 1 NaCr0 2 +4 H 20.


2

].

[Cr 2

3 Cl 2 +6

NaOH
3]

]+3 H 2 0. NaCl+[3 0]+3

H 0.
2

(5) (6)

]+[30]

NaOH+[2 Cr0

[2CrO,]. 2 Na 2Cr0 4 +2

H 0.
2

In making the complete equation, the reversible equation


is

(2)

omitted.

Chromates are generally


alkalies are soluble.

yellow.

Those

of

the

The

insoluble chromates react

with dilute acids, giving soluble products. " chromate is the pigment chrome-yellow."

Lead

PbCr0 4 +2

HN0 ;=! Pb(N0 +H CrO


3 3) 2 2

4.

464

MANGANESE AND CHROMIUM.


,

Potassium dichromate, K2 Cr2 7 forms large, red Sodium dichromate is crystals, which are soluble. often used in place of the potassium salt, because it Both chromates and dichromates is more soluble. are used in dyeing, in calico-printing, and as oxidizing Potassium dichromate is used in photogagents. " dichroraphy and to prevent polarization in the

mate "
is

battery.

When a chromate solution is treated with an acid, a dichromate


formed.

The

color

is

changed to

red,

owing to the formation

of

Cr 2

ions.

chromate.

We

Conversely, a base changes a dichromate to a can understand the relation of chromates to


if

dichromates better

we

acids as hydrates of their anhydrides, just as manganese acids (cf. 507).


(1) (2)

write the formulas of the corresponding we did with the

K CrG +2 HN0 ^= K Cr0 +Cr0 .H


2

KN0 +H Cr0 K Cr O +H 0.
3 2 2 2
7 2

(i.

e.,

Cr0 3 .H 20).

Potassium dichromate

is

thus an acid salt, but the form

KHCr04

loses water.

KHCr0

*
4

K Cr
2

+H 0.
2

While the reverse action, producing


is

KHCrO

4,

is

small,

it

appreciable; so that when potassium dichromate solution is added to the solution of a ionic metal that forms an insoluble

chromate, the chromate of the metal


(1)

is

precipitated.

K Cr
2

+H 0;zz(2KHCrO
2 4)

4 ).

(2)

AgNO,+ (2 KHCr0

Ag 2 Cr0 4 1 +2

KN0 +
3

HN0
2

3.

When a base is added to a

dichromate, the reversible equation,


7

K Cr
2

+H

KHCr0

4,

OXIDATION BY CHROMATES.
is

465
of

made complete, by the replacement


Hence a chromate
4

of the

H
2

KHCrO4

by

a metal.

is

formed.

KHCr0 +KOH
509. Oxidation

K Cr0 +H 0.
2 4

by Chromates and Dichromates. When chromic compounds are oxidized to chromates, a base is added, as well as an oxidizing agent; hence

when chromates or dichromates are used as oxidizing agents, i. e., are reduced, the operation is carried out in acid solution. The fundamental reaction is the
change of chromium trioxide to chromic oxide, with loss of oxygen (cf, 507) 2 Cr0 3 Cr 3 +3 0.
.

The oxygen unites with the reducing agent, while the chromic oxide reacts with the acid, giving a chromic salt. The reaction
between potassium dichromate,
ous acid (sulphur dioxide)
(1) (2)
is

dilute sulphuric acid,


:

and sulphur-

as follows
4

K
(2

+H S0 ;=
2
7)

(H 2Cr 2
3)

)+K S0
2

4.

(H 2Cr 2

(3)
(4)
(5)

Cr0 3 ) (OsO,)+3 H 2SO 4 3 H 2 S0 3 +(3 0)


is

H 0+(2 Cr0 + (3 0). (Cr


2
2

3 ).

Cr 2 (S0 4 ) a -f 3
3

H 0.
2

H S0
2

4.

When When
3
2

the solution
is

evaporated at the ordinary temperature,


.

chrome-alum

formed
is

alcohol

506) (cf. the reducing agent, equation

(5) is:

C H 60+(3

O)

C H4
2

(aldehyde) +3

H 0.
2

(cf.

Hydrochloric acid and potassium dichromate give chlorine 2 S0 4 in equa116). In this case, HC1 takes the place of

tions (1)

and

(4),

and

of

H S0
2

in equation (5).

466

MANGANESE AND CHROMIUM.


oxidizes

Hydrogen peroxide
acid,

a 'dichromate to perchromic

which

is

extracted from water solution


(cf.

by

ether,

and

colors

the ether blue

340).

510. Exercises. 1 Give the equations (a) Heating MnO and


.

for

Mn0

in air.

(6)
(c)

Oxidation of

Mn(OH) 2 by the air.


.

2.
(a)
(6)

Action of Mn0 2 with concentrated H 2 S0 4 Give partial and complete equations for:

With HC1.
3.

Heating a mixture of
:

Mn(N0

3) 2 ,

KOH, and KC10

4 in dilute sulphuric Treating the following with acid solution formic acid, sulphurous acid, ferrous chloride. 4 (c) Action of HC1 upon solid

KMn0
.

KMn0
2
3

Preparation of Cr 2 Remember that 4 C1


(cf)

from

K Cr

and

NH C1
4
2

505).

(e)

+HC1. Reaction between solutions of Cr(N0 3 ) 3 and


The same
for solutions of

NH

NH

K C0

3.

Cr2 (S0 4 ) 3 and (NH 4 ) 2 S. (g} Action of HC1 upon solid K 2 Cr 2 07. (h) Reaction when H 2 S is passed through a dilute sulphuric acid solution of KMn0 4 Through one of K 2 Cr 207. From Cr2 (S0 4 ) 3 (i) Preparation of K 2 Cr0 4 from CrCl 3
(/)
. . .

Exactly 20 c.c. of a solution containing 15.8 g. of KMn0 4 2 2 soluper liter were needed to react completely with some
3.

tion.

How much H

was there?

4. If 0.056 g. of iron

much
5.

KMn0

is

is dissolved in dilute sulphuric acid, how required to oxidize the resulting FeS0 4 to the

ferric state?

How could you prepare lead, calcium, and silver chromates?

Give the equations.


" " 6. What is meant by the of a voltaic cell? polarization To what is it due? How does K 2 Cr 2 7 prevent it? What chromium compound is formed in the " dichromate " batterv?

CHAPTER XXXVII.
LEAD, TIN,

AND PLATINUM.

511. Occurrence and Preparation of Lead. Lead occurs chiefly as galena, PbS, and is obtained from it by the following processes :

(1) If the ore is of high grade, it is first roasted in a reverbera462). By this operation part of the ore is tory furnace (cf. to the oxide, PbO, and part to the sulphate, PbS0 4 changed
,

while some remains unchanged.


(1)

(2)

2 PbS+3 PbS+2

2 2

PbO+2 S0
.

2.

PbS0 4

After the oxidation has gone far enough, the furnace doors are closed, and the mixture is heated without the admission of more
air.

The

lead oxide and sulphate then react with the unchanged


:

sulphide as follows
(1) (2) (2)

PbS+2 PbO PbS0 4 +PbS

3
-

Pb+S0 Pb+2 S0
2.

2.

If

the ores are poor, they are reduced in a blast-furnace,

or heated with iron.

PbS+Fe
(3)

FeS+Pb.
pay
for its extraction (base

If

there
cf.

is

enough

silver to

bullion;
(4)

Lead

462), the Parkes process is used. may also be made by the electrolysis of a mixture of

galena and dilute sulphuric acid. About 970,000 tons of lead were produced in 1910; 372,000 tons in the United States.
467

468

LEAD, TIN,

AND PLATINUM.
Lead
is

512. Properties

and Uses.

soft, blue-

gray metal, having a high luster which is soon tarnished by oxidation. The corrosion does not as with iron. Lead is not very malleable, penetrate, or ductile, but it can be rolled into sheets, and
pipe.
forced, while hot, through steel dies, forming lead It melts at 327 C.

++
Lead
(i.e.,

lead ions, Pb)

is

tions of its salts

by such metals

readily displaced from the soluas zinc and iron (cf. 180).

It often separates in a branching, crystalline form,

known

as a

lead tree.
nitrate.

Nitric acid reacts readily with lead, forming the Dilute sulphuric attacks it very slowly; the hot, con-

centrated acid acts as upon copper (cf. 265). When lead is boiled with concentrated hydrochloric acid, hydrogen is formed,

but very slowly. Many organic acids, e. g., acetic acid, act upon it, in the presence of air, to form soluble salts.
All compounds of lead are poisonous. When even small amounts of lead are taken regularly into the body, as in drinking water, the lead accumulates until it causes sickness. Painters " are subject to painter's colic," because of the lead compounds in paint. Lead is almost unaffected by pure water, if air is not
present; but air

and

soft

which

is

slightly soluble.

water together produce lead hydroxide, The presence of carbon dioxide makes

more readily with water. Hard water acts upon lead very slightly, because a coating of lead carbonate and sulphate soon protects it from further action. Great care should
lead react even

be exercised in using water that has run through new lead pipes. Besides being used for conveying water, lead pipes are used
as sheaths for the cables of telephone wires. In sheet form, the metal is used to line the " leaden chambers " (cf. 262), and the inside of vats and tanks used for other chemical processes.

Large quantities of

it

are

made

into shot

and

bullets, the plates

LEAD COMPOUNDS.
of storage batteries, pewter, fuse wire, etc.

469
solder,

and
(cf.

alloys, such as type-metal,

370, 374,

and

515).

Shot contains

about 0.5% of arsenic.

513.

Lead Compounds.
salts

In

its

common

salts

plumbic

lead

is

bivalent.

These are made

monoxide (PbO) with acids. Lead hydroxide, Pb(OH) 2 is both a base and a weak acid

by

treating lead

(plumbous acid).
Lead monoxide
exists as

a yellowish-red, crystalline mass

("litharge"), and also as a yellow powder ("massicot"). Litharge is made in large quantities in the separation of lead and
silver

462). Massicot may be made by heating lead nitrate (cf. " " or carbonate. A mixture of lead oxide and glycerine sets to

a hard, compact mass, and is used as a glass cement. Lead oxide is also used in making glass (cf. 394), glazes for pottery ( 479),

and
"

for varnishes.

Red

oxidized

by heating
oil

lead," or minium (Pb 3 4 ) is made it in the air to 400 C.

when

litharge

is

mixture of red

lead and linseed


oil

by the lead compound

hardens rapidly, owing to the oxidation of the (cf. 31); hence it is used to make

tight joints in gas pipes, etc. red paint for iron work.

Minium

is

also used to

make a

Lead

dioxide,

Pb0

2.

When

red lead

is

treated with dilute

remains as a brown powder. Both red lead and the dioxide react with hydrochloric acid to give chlorine. Lead also forms a suboxide, Pb 20, and a trioxide, Pb 2 3
nitric acid, lead dioxide
.

Lead
acid;

nitrate,

Pb(N0 3 ) 2

is

made from

litharge

and

nitric

lead acetate, Pb(C 2

acetic acid.

acetate

is

2 0, from 3 2 )2. 3 litharge and are white, crystalline, and soluble. Lead " called sugar of lead." Lead sulphate (PbS0 4 ) and

Both

lead chromate (PbCr0 4

cf.

508) are insoluble in water.

Lead

470
sulphate
267).
is

LEAD, TIN,
somewhat

AND PLATINUM.
(cf.

soluble in concentrated sulphuric acid

Lead

chloride,

in cold water,

PbCl 2 forms white crystals, difficultly soluble but soluble in hot water. The iodide, PbI 2 forms
,
,

glistening, yellow crystals.


,

It is less soluble

than the

chloride.

Lead tetrachloride, PbCl 4 is a yellow liquid obtained when lead dioxide is treated with very cold, concentrated hydrochloric
acid.
It is

chlorine.
138).

unstable, breaking down into lead chloride and The corresponding MnCLj has never been made (cf.

Lead sulphide, PbS,

is

obtained as a black precipitate

when a

++
solution containing ionic lead (Pb)
ionic sulphur (S).
is

treated with one containing

The

free elements also unite directly.

Lead

sulphide
salts

is

oxidized to the sulphate


,

when heated

in the air.

Lead carbonate, PbC0 3 is precipitated from solutions of lead by ammonium carbonate or sodium bicarbonate solutions. The normal carbonates of sodium and potassium precipitate basic lead carbonate. White lead is a mixture of basic lead
. .

the chief one being Pb(OH) 2 2 PbC0 3 Several in making it; the oldest and best is the Dutch " " process. In this process gratings or buckles of lead are placed in earthenware pots containing a little vinegar, or dilute acetic
carbonates,

methods are used

acid. The pots are placed in layers, covered with planks, and buried in manure. The fermentation of the manure produces " " heat and carbon dioxide, and the lead buckles are converted, in three or four months, into the white basic carbonate. The

reactions are essentially as follows

(1)

Pb+O
.

(from

air)

+HC H
2

>

Pb(OH)C 2 H 3
Pb(OH),. 2

(basic

acetate)
(2)

Pb(OH)C 2H 3
2
3

+2 C0

+H

PbC0 3

+3 HC H

2.

The French process

consists in passing carbon dioxide into a

LEAD COMPOUNDS.
solution of basic lead acetate.

471

The process is rapid, but the product is considered inferior to Dutch white lead. There is also an electrolytic process. This consists in passing a current, between lead electrodes, through a solution containing
nitrate (or chlorate) and sodium bicarbonate. process is continuous, for sodium nitrate is regenerated. lead is precipitated.

sodium

The
White

White lead
"

"
covering

used for paints because of its opaqueness, or power. It is ground up with linseed oil. An obis

jection to

it is

that

it

hydrogen sulphide.
white
"

turns "

brown

Zinc white

or black in the presence of " "

(BaS0 4 )

are not blackened

by

(ZnO) and permanent 2 S, but they have not

nearly the covering power of white lead.

Plumbites and Plumbates.


lead oxide or hydroxide
"

Plumbites are formed when


"
in
2

dissolves
7

an excess
2 2

of

an

alkali.

HaPbOH-2 NaOH
form (H 4Pb0 4 ) and
is

Na Pb0 +2

H 0.

" " Plumbic acid forms plumbates derived from both its ortho " its meta " form (H 2Pb0 3 ). Its anhydride

lead dioxide,

Pb0

2.

This

"

dissolves

"

in caustic potash

solution, giving potassium plumbate.

KOH+PbO

K Pb0 +H 0.
2

Both red lead and lead

trioxide give lead dioxide

when treated

with dilute nitric acid; hence they are considered to be lead n orthoplumbate (Pb 2 .Pb0 4 ) and metaplumbate (Pb".Pb0 3 ) respectively.

Storage Battery.

The common
in the

two lead plates made


dilute sulphuric acid.

The

divided lead (made by contain lead dioxide. The current owes

grids," and a bath of grids of one plate are filled with finely reduction); while those of the other

form

of

storage battery consists of "

its

maintenance to the

oxidation of the finely divided lead on the one plate to PbO, and the consequent reduction of the Pb0 2 of the other plate

472
to

LEAD, TIN,

AND PLATINUM.
PbO
of

PbO.

Of course the acid present converts the

both

plates into battery are:

PbS04

The

equations for the discharge of the

(1) (2)

Pb0 2 +H S0 4
2

Pb+(0)+H S0
2

PbS0 4 +H 0+(0). PbS0 +H 2O.


2
4

The battery is recharged by passing a current into it so as to reverse these changes, and to restore the plates to their original
condition.

514. Occurrence and Metallurgy of Tin. source of tin is cassiterite, or tin-stone, Sn0 2

--The
.

This

in Alaska, Cornwall (England), Germany, Australia, and in Billiton and Banca, islands east of

occurs

Sumatra.
Tin was known in very early times. The alloy bronze, conand tin, was used before iron, and gave its name " Bronze Age." Although tin has been carried away to the from Cornwall since ancient times, the mines are still productive.
sisting of copper

The metallurgy

of tin consists,

first,

in roasting

the ore, so as to oxidize and remove arsenic and The tin oxide is then reduced with coal in sulphur.

a furnace, the metal being drawn off and cast into bars. These bars of impure tin are then slowly heated on a sloping hearth. The tin melts and runs down the hearth, leaving the unmelted impurities

Banca tin is the purest. That from Germany and England usually comes in blocks, whence
behind.

the

name block tin.

PROPERTIES AND USES.


515. Properties

473

having a

and Uses. Tin is a white metal, which does not tarnish in It is soft and malleable, and melts at the air. 233 C. The ordinary form changes into a gray, brittle form at low temperatures; hence tin organbrilliant luster

tin disease pipes, gutters, etc., are subject to in cold winter weather. The ordinary form

"

"
is
it

stable

above 20

C.

When

a bar of tin
"),

is

bent,

emits a grating noise (" cry of tin to the friction between its crystals.

probably due

Tin burns, when


oxide,

sufficiently heated, giving stannic

SnO2

With

hydrochloric

acid

it

gives

stannous chloride (SnCl2 ) and hydrogen. Hot, concentrated sulphuric acid produces stannous sulphate

(SnS0 4 ) and sulphurous


.

acid.

Concentrated

nitric

acid oxidizes tin to an insoluble, white solid, metaThe dilute acid gives stannic acid (H2 Sn0 3 ) 5 stannous nitrate, Sn(N03) 2 and ammonium nitrate
,

(cf.

227, end).
of Tin.

Uses

The

chief use of tin

is

to coat iron, brass, and

copper. Tin-plate, made by dipping iron into melted tin, is the " " cans and cooking utensils. Owing to its tin material of
is the greatest tin-consumbrass wire (copper and zinc), of Pins are made ing country. and are coated with tin by dipping them into the solution of a

canning industries, the United States

tin salt.

Copper
(cf.

utensils are also tinned to prevent corrosion.

Tin
"
alloys

is

a constituent of
374),

many

alloys,

among them
and

"fusible

bronze,

bell-metal,

Britannia metal

Solder usually contains 50% tin and 50% is about 90% tin, 8% antimony, and

gun-metal (q. v.). lead (cf. 100, end).

2% copper.

474
Pewter
as tin
is

LEAD, TIN,

AND PLATINUM.
lead.

75%

tin

and

25%

Tin

is

also used for pipes

and

foil.

pounds, in

Tin forms stannous comCompounds. which the metal is bivalent, and stannic compounds, in which it is quadrivalent. It also forms stannites and stannates.
516. Tin
,

Stannous chloride, SnCl 2 is formed from hydrochloric acid and an excess of tin. A little acid is added from time to time to react with the tin, and to keep the solution in reduced, i. e.,
stannous, form.
crystals (SnCl 2 2
.

Evaporation of the solution leaves colorless H 20). Stannous chloride is easily oxidized to

stannic chloride, and is, therefore, a reducing agent. It reduces mercuric chloride, first, to mercurous chloride, and then to mercury 181). It reduces ferric to ferrous salts (cf. 491). In the (cf.

presence of acid, the air oxidizes chloride is used as a mordant (cf.

it

to stannic chloride.

Stannous

477)

Stannic chloride, SnCl 4

with aqua regia.


liquid,
is

made, in solution, by treating tin is a colorless, fuming made by passing dry chlorine over heated tin. Its solution
,

is

The anhydrous substance

hydrolyzed.

SnCl 4 +4

HOH
is

"

Sn(OH) 4 +4 HC1.

Stannous oxide (SnO)

a black powder made by heating


(cf.

stannous oxalate, or hydroxide, out of contact with air

287).

SnC 2

SnO+CO T +C0

Stannous hydr oxide, Sn (OH) 2 or 2 0. 2 SnO, is formed as a white precipitate when a stannous salt is treated with sodium
carbonate.
(1) (2)

SnCl 2 +Na 2 C0 3

NaCl+(SnC0 3 ).
Sn(OH) 2 1

(SnC0 3 )+2HOH

+H C0
2

3.

TIN COMPOUNDS.

475

caustic alkalies.

The hydroxide gives soluble stannites when treated with The stannites are reducing agents. Stannic oxide, Sn0 2 is made by burning tin or stannous oxide (SnO), and by heating stannic acid. Sn0 2 shows its acid char,
. ,

acter, and its analogy to C0 2 Si0 2 and Pb0 2 by reacting with molten alkalies to form stannates, e. g., Na 2Sn0 3 Stannic acid, if it could be obtained as a definite compound,
,
.

would be H 4 Sn04 or H 2Sn0 3 It loses water, giving its anhydride, Metastannic acid is its insoluble polymer, (H 2 Sn0 3 ) 5 Sn0 2
.

[cf.

219].

When

fused with alkalies, metastannic acid gives

sodium stannate.

This can be obtained as crystals,

Na2Sn03

3H 0.
2

tin

Stannous sulphide, SnS, is a brown powder, formed by heating with sulphur, or by passing hydrogen sulphide into a solution
stannous
salt.
,

of a

Stannic sulphide, SnS 2 is a yellow solid, made from hydrogen sulphide and a stannic salt, and used as a pigment (" mosaic

When heated, it gives stannous sulphide and sulphur. "). Sulphostannates are formed by the union of the tin sulphides with soluble sulphides, e. g., Na 2S. With SnS a polysulphide 419 and 427) must be used. (cf.
gold

SnS 2 +Na 2S

SnS+Na S+S
2

Na 2SnS3 Na SnS3
.

Sulphostannates of the alkali metals are soluble; hence the tin sulphides, like those of arsenic ( 365) and of antimony

Gold sulphide (Au 2S3 ) in alkali sulphides. and platinum sulphide (PtS 2 ) act in the same way. Sulphostannates react with strong acids, giving sulphostannic add, H 2 SnS3 This is unstable; the metal sulphide and hydrogen sulphide are
(

"

369)

dissolve

"

formed

(cf.

365; also
2 3

H C0
2
2

3,

282).

Na SnS +2 HC1
(H 2 SnS 3 )

(H 2 SnS 3 )+2NaCl.
2

H S T +SnS

476

LEAD, TIN,

AND PLATINUM.

517. Platinum; Occurrence and Preparation. " Platinum is found native (cf. Electromotive Series/ 405 and Appendix x), but only small deposits are known. Some is found in Australia and California, but most of it comes from the Ural Mountains
7

(Western Siberia).
is usually mixed with five other rare metals, belonging to the eighth periodic group. These are: palladium, ruthenium, rhodium, osmium, and iridium. About 75% of the

Native platinum

all

ore

is

The

platinum. ore is treated with aqua regia, which reacts with the

platinum and some iridium. The resulting chlorplatinic acid, H 2PtCl6 (cf. 519), is treated with ammonium chloride, producing

precipitate

of

ammonium

chlorplatinatc
results.

When

this is heated strongly,


is

quantity of iridium

platinum not removed.

(NH^PtClc. The small

Platinum is a grayish518. Properties and Uses. white metal, of high luster, and of specific gravity 21.5. Air has no action upon it, and the temperature
oxy-hydrogen flame is needed to melt it. Platinum does not react with the common acids, but is attacked by aqua regia and by chlorine- and bromine-water. Fused alkalies react with it, giving platinates, but alkali carbonates do not.
of the
Finely divided forms of the element are known as platinum black and platinum sponge. Platinum black is made by reducing a platinum compound in solution, as when zinc is added to
chlorplatinic acid; the spongy form, by heating Both of these are active catalyzers (cf. 260).

(NH^PtCle. Owing to its

EXERCISES.

477

power of condensing oxygen on its surface, and of occluding hydrogen (cf. 53) platinum in finely-divided form causes instant union of the oxy-hydrogen mixture. The resistance of platinum to most chemicals, and its high
,

very useful in the laboratory. It is used Large retorts of platinum are used foil, crucibles, wire, etc. in concentrating and distilling sulphuric acid (cf. Be263). cause it expands at the same rate as glass, platinum wire is melted into the glass of incandescent lamps to give connection
melting point,
it

make

as

with the carbon filament inside the lamp. Platinum vessels should never be used for heating substances that can set free phosphorus, silicon, antimony, lead, or, in general, any of the
metals; neither should they be heated in smoky flames. When platinum is treated with aqua Chlorplatinic Acid. the chloride (PtCl4 ) formed unites with hydroregia, platinum
chloric acid, giving chlorplatinic acid,
for

H PtCl
2

6.

This

is

used

"toning" platinum photographs


potassium

(cf.

466).

The
,

solution

and with ammonium potassium chlorplatinate, K 2 PtCl 6 and of ammonium chlorplatinate, (NH 4 ) 2PtCl 6 respectively. The sodium
of this substance gives with
salts precipitates of

salts

salt

is

soluble.

solution of chlorplatinic acid thus serves as a

+
test for potassium salts (K), even

when sodium salts are present.

519. Exercises.
i.

Write the equations for the following reactions:

(a)
(6)
(c)

Lead acetate and

zinc.
air,

Lead, in presence of

Lead, in presence of
"

(d)
(e)

and acetic acid. and excess of C0 2 Litharge and sand; red lead and hydrochloric
air,
.

acid.

Solution

"

of lead sulphate in concentrated

H S0
2

4.

(/)

(0)

Qi)

Lead chloride and potassium iodide solutions. Lead nitrate and sodium bicarbonate solutions. Red lead and dilute nitric acid.

478
(i)

LEAD, TIN,

AND PLATINUM.

Tin and concentrated, hot sulphuric acid. Tin and dilute nitric acid, (fc) Tin and concentrated nitric acid. (0 Brass and stannous chloride. (m) Mercuric chloride treated with a little of stannous chloride; with an excess.
(j)

(n) Acidified
(o)

stannous chloride in contact with

air.

Auric sulphide (Au2S 3 ) and

ammonium

sulphide.

(p)
(q)
(r)

Platinum sulphide (PtS 2 ) and potassium sulphide. Platinum and carbon (hot),
Effect of heating

ammonium

chlorplatinate.

would you distinguish lead from tin? From zinc? From aluminum? From iron? From platinum? " " and " permanent-white " zinc-white 3. Why are not
2.

How

affected
4.

of tin

by hydrogen sulphide? Give the chemical reasons for the objection to an alloy and lead as the protective covering of iron cooking utensils.
iron.

For the objection to galvanized

CHAPTER XXXVIII.
SOME CARBON COMPOUNDS.
It was formerly be520. Organic Chemistry. lieved that the complex substances produced by

animals and plants, such as sugar, starch, uric acid, etc., could not be made in the chemical laborahence there arose a distinction between tory; " " and " inorganic " compounds. Organic organic " " compounds, it was thought, needed vital energy for their formation, while inorganic substances could be made without the intervention of living
things. However, the preparation of urea, CO(NH2 ) 2 an animal product, by Wohler in 1828 and the many organic syntheses made since that time have de,

stroyed the force of this distinction. At the present " " is practically time the term Organic Chemistry " ComCarbon of the to Chemistry equivalent

pounds/'
The carbon compounds exceed
in

number those

of all the

other elements together, yet each substance is composed of relatively few elements. Many compounds contain only carbon
larger number, carbon, hydrogen, and important organic substances contain carbon, hydrogen, and nitrogen, while others have oxygen in addition.

and hydrogen; a much


oxygen.

Many

Phosphorus, sulphur, and the halogens are also present in


organic compounds.
479

many

480

SOME CARBON COMPOUNDS.


described in
this

The compounds
(4)

chapter are

classified as (1) hydrocarbons,

(2) alcohols, (3) ethers,

aldehydes,

(5) acids, (6)

organic salts, or esters,


(8)

(7)
(9)

amines and alkaloids, phenol derivatives.

carbohydrates, and

Sub521. Hydrocarbons of Marsh Gas Series. stances composed of only hydrogen and carbon are
called

hydrocarbons.
in

mentioned
the
first

have already been 291 to 297. Methane (291) is


Several

member
differs

or paraffin series

of a large series the marsh gas, in which the formula of each

member

from that of the next member by


be homologous.
of

CH

Such a

series is said to

The names and formulas


paraffin series are

some members

of the

companying of hydrogen atoms in the molecule of each of these hydrocarbons is two more than twice the

given in the first column of the actable. The formulas show that the

number
number

of carbon atoms;

hence the "series

represented by the general formula C n 2n +2. To explain the fact that so large a number of

may

be

marsh gas hydrocarbons exists, chemists have assumed that carbon is tetravalent in these compounds 133 and 135), and that the carbon atoms are (cf.
united in chains.

The
(cf.

constitutional formula for


.

marsh gas has been given

218)

That

of ethane

is

ETHYLENE AND ACETYLENE.

481

H H H C C
H; that
of propane,

H H H
H C C C

H.

MARSH GAS
SERIES.

482

SOME CARBON COMPOUNDS.


G2H2+2 H2

C H +2 Br
2 2

Because of their ability to unite with hydrogen, etc., to form marsh gas derivatives, both ethylene

and acetylene are said to be unsaturated, to distinguish them from methane and its homologues, which
are saturated.
in these

explain the unsaturation existing compounds by assuming that all the valences

We

of the carbon
Ethylene
is

atoms are not used.


by the
constitutional formula,

represented

H
by H

H
;

)c=c( H/ \H
acetylene

C ^C

H.

The homologues of ethylene and acetylene contain chains of carbon atoms with both saturated and unsaturated groups.
Thus, the constitutional formula of butykne (see table)
is

H H
C

H
C
i

H H
C = C.
I

H
523. Closed

H
The
chains of

and Open Chains.

carbon atoms in substances already described are " " called chains to distinguish them from open " " of atoms in closed groups rings, which are called
chains.

The polymethylene and

benzene derivatives

named

in the table contain closed chains.

BENZENE HYDROCARBONS.
Thus, the constitutional formula
of tetramethylene is
2
'

483

HC
2

CH CH

HC
2

/CH = C
that of benzene.

HC<x

X5H-CH/

In thiophene,

a sulphur atom forms part of the

ring.

In 297 it was 524. Benzene Hydrocarbons. stated that benzene is obtained from coal tar.

When

the coal tar

is distilled, it

yields several fracconsist


of

tions the lower of

which contain benzene and toluene,


xylene,

while higher-boiling portions naphthalene, anthracene, etc.

Benzene
at 80

is

C. and does not

a colorless, aromatic liquid which boils mix with water. It burns

with a smoky flame. Solid benzene melts at 6 C. Benzene is used as a solvent and as a source of

benzene derivatives, chiefly nitrobenzene,


(cf.

H NO
6

232).

Nitrobenzene is a yellow liquid boiling at 205 It has the odor and taste of bitter almonds.
Toluene
.

C.

It boils at 110. is methylhenzene, C 6H 5 CH 3 Napthalene, Ci H 8 is a white solid melting at 79 and boil" moth balls " and in the preparation ing at 218. It is used for of dyes. It reacts with bromine according to the equation,
,

CioH 8 +Br 2

>

C 10H 7Br+HBr.

484
This
is

SOME CARBON COMPOUNDS.


a good laboratory method for generating hydrogen
(cf.

bromide

321).

Anthracene, CioH 14, is a white solid melting at 213 and boiling about 350. It is used as a source of the valuable red dye alizarin, which occurs naturally in madder root. Turpentine is a resinous substance obtained from incisions
bark of pines. By distillation it yields oil of turpentine, which consists largely of a hydrocarbon, CioHi6 (cf. 121).
in the

The residue is rosin.


525. Petroleum.

Petroleum

is

thick,

oily

It liquid obtained from the earth in many places. of a mixture consists essentially of hydrocarbons, with larger or smaller amounts of nitrogen and sulphur compounds. The largest deposits are in the

United States and Russia, but it occurs also in Japan, India, and Austria. In 1911 the United States produced about 220,000,000 barrels of the crude oil, valued at about $135,000,000.
It is uncertain

decomposition of

how petroleum was produced, whether by the animal or plant remains or by the action of
upon
carbides,

water, under great pressure, carbide of iron.

particularly the

Aluminum

carbide and water react according to the equation,

A1 4 C 3 +12

HO
2

>

4 Al(OH) 3 +3

CH

4.

is used as a but most of it 298), (cf. is refined. The petroleum is carried from the wells In to the refineries through long systems of pipes. the refining process it is shaken successively with

Refining.

Some crude petroleum

fuel

and

to enrich water-gas

ALCOHOLS.

485

sulphuric acid, caustic soda or potash solution, and water. It is then distilled, and the distillates which

pass over between certain degrees of temperature are collected by themselves. Thus many fractions
are obtained.

The lowest fraction boils about


This
is

18 C.,

and

is

called rhigolene.

agent.

Between 18

and

used as a refrigerating 250 gasoline, benzine

(not benzene), petroleum ether, ligroin, kerosene, etc., are collected. They are used as fuels and solvents.

The higher-boiling products are converted into mineral lubricating oils, vaseline, and paraffin (white wax). Coke remains in the retort. Over two
hundred commercial products are now made from
petroleum.
526. Natural Gas.
tible

In many places a combus" in has collected large, underground pockgas

ets,"

and

is

released

by

drilling wells.

The gas

consists largely of methane (cf. 292), and is carried to consumers in pipes, as in the case of illuminating
gas.

The value

of the natural gas produced in the

United

States in 1910

was nearly $71,000,000.

The alcohols form a large and 527. Alcohols. important class of organic substances, and include
homologous series. The first member of one of these series is methyl alcohol, CH 4 O, and its second member is ethyl alcohol, C 2 H 6 O. Methyl " wood spirit," because it is obtained alcohol is called
several

486

SOME CARBON COMPOUNDS.


It boils

in the dry distillation of wood (cf. 275). at 66 C. Ethyl alcohol boils at 78 C.


colorless liquids.

Both are

The
(cf.

alcohols react with metals

much

as water does

74).

sodium

ethylate
2
2

Thus, ethyl alcohol and sodium produce and hydrogen.


6

C H 0+2 Na

C 2H ONa+H
5

2.

acids the alcohols react like hydroxides of the metals, giving salts and water.

With

CH 0+HN0 2 C H 0+H S0
4
3 2

CH N0 (C H
3
2

(methyl nitrate)

+H O.
2

5) 2

S0 4

(ethyl sulphate)

+2 H 0.
2

These equations are like those for the reactions of potassium and sodium hydroxides with the acids 160 and 226), consequently the alcohols are (tflooked upon as hydroxides. The formula of methyl
alcohol
is,

therefore, written

CH OH,
3

or

H
i

H,

H
and that
of ethyl alcohol,

C
"

H OH
6

(cf.

group CH 3 is the radical methyl (cf. 210), and methyl alcohol is methyl hydroxide. The radical
"

220).

The

CH
2

ethyl." properties of the first five alcohols of the series are given in the table.
5

is

called

"

Some

PREPARATION OF ETHYL ALCOHOL.

487

ALCOHOL.

488

SOME CARBON COMPOUNDS.

allowed to sprout and develop far enough to change much of their starch into sugar. This is then fer-

mented by adding

Besides alcohol and yeast. carbon dioxide, small amounts of glycerine and of The propyl, butyl, and amyl alcohols are formed.

mixture of these alcohols

The

ethyl alcohol

is

" fusel oil." separated from most


is

called

of the

water and fusel oil by distillation, but the product " alcohol) still contains from four to (" 95 per cent This may be almost entirely ten per cent of water. removed by distilling the commercial alcohol with
lime.

The

distillate is called absolute alcohol.

529. Liquors. Wines are prepared by allowing the ferments present in the air (cf. 190) to act upon the juice of grapes. Beers are produced in a similar way from hops and malt (sprouted barley) When the fermented solution contains from 10 to 14% alcohol,
.

action of the yeast ferment stops entirely. Liquors containing a larger proportion of alcohol have been distilled, or the alcohol

has been added directly. The colors and flavors of liquors are due to substances present before fermentation or produced while
the liquor stands in casks, or to foreign substances added. Beer has ordinarily from 3 to of alcohol; wine, 5 to

7%

20%;

and whiskey, gin, and rum, above 40%. In dilute form, alcohol acts as an intoxicant; undiluted, it is a poison.

C3 8 3 530. Glycerine. Glycerine is a sweet, colorless, viscous liquid produced by the hydrolysis of
.

fats

(ef.

in water

413 and 540). It is soluble in alcohol and and absorbs moisture from the air. It is

ETHERS.

489

used in making nitroglycerine (cf. 232), soaps, cosmetics, and inks; also as a food preservative and a lubricator. It boils at 290 C.
Glycerine
is

a complex alcohol.

Its constitutional

formula

is

H H
H H
C C
C

OH
OH

OH

ROH
R O.
2

If represents an organic radical, 531. Ethers. is the general formula of an alcohol (cf. table,

527).
If

We
the

represent an ether

of
if

2 2

is

CH

3,

by R we have

R, or
the formula

of methyl ether; methyl ether see

5,

that of ethyl ether.

For

220.

sulphuric Ethyl ether, (C 2 5 ) 2 O, is also called ether/' It is a colorless, volatile liquid having a sweet odor. It boils at 35 C., is very inflammable,
for organic compounds. Ether is used in surgery as an anesthetic. For its solubility in water see 82.
is

"

and

an excellent solvent

Ether is made in the laboratory (Fig. 91) by Preparation. of ethyl alcohol and sulphuric acid to 140 mixture a heating (not higher) and keeping it at this temperature while adding
alcohol in a slow stream through a separatory funnel. The mixture of alcohol and ether which distills off
tilled carefully.
is

redis-

The rubber tube attached

to the receiver (see

490
Fig. 91)

SOME CARBON COMPOUNDS


carries any uncondensed vapor The equations are
:

of ether

away from

flames.

1.

2.

C 2H OH+H2S0 4 C 2H OH+C 2H HS04


5 5 5

C H HS0 4 +H
2
5

0.
2

(C H 0+H S0
2
5) 2

4.

C H HS0
2

is ethyl

hydrogen sulphate

(cf.

164).

FIG.

91.

The oxidation of ethyl alcohol 532. Aldehydes. a of mixture by potassium dichromate and dilute
sulphuric

acid

called, also,

produces acetaldehyde, simply aldehyde (cf. 509).

CH CHO;
3

/OH CH CH( +0
3

>CH CH (
3

/OH
X)H

+H 0.
2

Aldehyde is a colorless and very soluble in water.

liquid boiling at 21
It is

C.

reduced by nascent

ALDEHYDES.
hydrogen
(cf.

491

123),
it

oxidizing agents

giving ethyl alcohol. gives acetic acid.

With

+0
)

CH C /OH
3

'

\>

taining

Aldehyde is used to reduce silver solutions con" " of mirrors ammonia, as in the silvering " " The name is derived from (cf. 464). aldehyde

=
FIG.
92.

al(cohol) de hyd(rogenatus), of hydrogen."

"
i.

e.,

alcohol deprived

Formaldehyde, H2 C = O, is made by the oxidation of methyl alcohol. The laboratory method (Fig. is to air draw 92) through warm methyl alcohol and then to draw the mixture of air and alcohol vapor over heated copper.

CH OH+0
3

H CO+H O.
2 2

492

SOME CARBON COMPOUNDS.


is

Formaldehyde
soluble in water.

It is

a colorless, irritating gas, very used as a disinfectant and


is

preservative.

Formalin

40%

solution of for-

maldehyde. Benzaldehyde, C 6 H 5 CHO (see table, 538), is the oil of bitter almonds found in almonds and cherry It has a pleasant odor, boils at 179, and kernels. is used as a flavor.

When marsh gas is 533. Halogen Derivatives. treated with chlorine in diffused light, the products
are methyl chloride (chlormethane)
acid.

and hydrochloric

CH +C1
4

CHsCl+HCl.

Under proper conditions the reaction may go


further,

giving

dichlormethane

(CHsClg),

trichlor-

methane (CHC1 3 ), and even tetrachlormethane (CC1 4 ). Methyl chloride is gaseous at ordinary temperatures; the others are colorless liquids. Trichlormethane is
chloroform, the anesthetic 63 C.
(cf.

389).

It

boils

at

Chloroform is generally prepared by the action of bleaching powder upon alcohol or acetone, (CH 3 ) 2 CO. It may also be made by the action of alkalies upon chloral (trichloracetaldehyde),

CC1 3 CHO.
Chloral
is

made by

the action of chlorine upon alcohol;

it is

a liquid with a disagreeable odor. Like other aldehydes combines with water, giving a hydrate. Chloral hydrate often used by physicians to produce sleep.

it
is

ACETIC ACID.
,

493

lodoform, CHI 3 is analogous to chloroform. It is a yellow solid, melting at 119. It is used as a


surgical dressing.

The organic acids are 534. Organic Acids. oxidation products of the corresponding aldehydes.
While the general formula of aldehydes
is

C^
may
of

/H ^O

X)H
that of acids
is

C^
X)
etc.

The

acids

be

mono-,

di-,

tri-basic,
is

The hydrogen
(cf.

the

CO.OH

group

the ionic hydrogen

176).

158 and Acetic acid (cf. 535. Acetic Acid. of The wood. distillation the formed is dry by 275) crude product (pyroligneous acid) is neutralized with
lime or caustic soda.
purified
acid.
etc.,

The

resulting acetate

is

then

The

and treated with concentrated sulphuric reaction is like that between chlorides,
(cf.

and sulphuric acid

225).

\)Na
sodium
If
acetate

+H S0
2

is

CH C
3

+NaHS0

4.

acetic acid

the acetate used

anhydrous the acid

is

ob-

tained as a sharp-smelling liquid which solidifies tq

494

SOME CARBON COMPOUNDS.


about 17 C. (glacial C. and mixes readily

colorless crystals melting at

acetic acid).

It boils at

118

with water.
Sodium
acetate,

NaC H
2

2 -f

H 0,
2

is

a white solid used in

making dyes. It loses its crystal water when heated. Lead acetate, Pb(C 2 H 3 2 ) 2 +3 H 2 (cf. 513), is used in in lead chromate and (chrome yellow) making dyeing ( 508) Impure iron and aluminum acetates are used as mordants in dyeing and in the printing of calico.
.

Verdigris, used for a blue paint, is basic copper acetate. Pan's green, an arseno-acetate, was mentioned in 363.

536. Formic Acid,


in stinging nettles

H 2 C0 2 Formic acid is found and the bodies of red ants. It is


.

prepared by heating oxalic acid with glycerine.

HC
2

H C0 +C0
2
2

2.

The anhydrous
100.
It

acid melts at 4

C. and boils at

produces blisters on the skin.

As was stated in 280 and 528, 537. Vinegar. a ferment in yeast decomposes sugar, giving alcohol and carbon dioxide. If the dilute, impure alcohol
(wine or cider)
is

allowed to stand in the

air,

a new

fermenting agent ("mother of vinegar") oxidizes it to aldehyde and acetic acid. The dilute, impure
acetic acid that results
is

vinegar.

On a large scale, vinegar is made in casks or vats filled with shavings and perforated so that air has free access. The shavings " " are inoculated by means of strong vinegar, and the dilute
is

allowed to trickle over them,

OTHER ACIDS.
538. Other Acids.

495

Acetic and formic acids are

the

first

relation

members of an homologous series. The between some of these acids and the cor-

responding hydrocarbons, alcohols, and aldehydes is shown in the table. All except the last two are derived from marsh gas hydrocarbons.
HYDROCARBON.

496
is

SOME CARBON COMPOUNDS.

obtained from the walls of wine casks as a dark solid called


is

"

tartar" or"argol." From this the acid " see 369. "tartar emetic

prepared.

For

Malic acid,
Citric acid,

H C4H
2 3 6

5,

occurs in fruits.

It

forms deliquescent

crystals melting at

100.
7

H C H5O +H 0,
2

forms crystals melting at 100.


fruits.

It occurs in lemons, oranges,


citrate is

and other acid

Magnesium

a medicine.

Alcohols react with acids (cf. water and organic salts, or estei 527) producing Thus acetic acid and alcohol produce ethyl acetate
539. Esters.

and water.

CH COOH+HOC H
3

CH COOC H +H 0.
3 2
5

The

reaction

is,

however,

reversible:

water

To make the forma413). saponifies the ester (cf. tion of the ester complete we remove the water from " " the sphere of action by means of concentrated
sulphuric acid. Alkalies the esters more rapidly

and

dilute acids saponify

than water.

For ethyl
is
:

acetate and sodium hydroxide the equation

CH COOC H +NaOH
3

CH COONa+C H OH.
3 2 5

Many

esters present in fruits

and flowers give to them a


used

characteristic odor

and

taste.

Artificial esters are often

instead of the natural flavors in the preparation of drinks, Thus ethyl butyrate has the odor and extracts, and perfumes.
taste of pineapples;
anate, that of apples.

amyl

acetate,

that of bananas; amyl valeri-

AMINES.

497

The most important 540. Fats and Oils; Soaps. esters are the natural fats and oils, which consist
essentially of the glycerine esters of stearic, oleic, and palmitic acids. These esters are called stearin,

and palmitin, amount of olein present


olein,

The relative respectively. in the fats largely determines their fluidity, since olein is liquid at ordinary temThe other two
esters are solids.
oil is

peratures.

Talloiv

and beef-suet are largely stearin; palm palmitin; lard and olive oil contain
while butter
acids.
is

largely
olein;

much

a mixture of several

fats,

esters of

palmitic, stearic, oleic, butyric, caproic,

and capric
5

The
9 9

last

two have the formulas


respectively.

C HnCOOH

and

C Hi COOH,

413) the alkali and the fat are Soap. In making soap (cf. heated in large kettles until the fat is saponified. The soap remains in solution until salt is added, which makes it rise to

the top of the mixture. The salty solution is worked up for glycerine, while the soap is washed, perfumed, and colored, or " " with borax, sand, etc. It is then cut into bars and filled
dried.

Hard soaps
potassium

consist of the

sodium

salts,

and

soft soaps of the


oil,

salts of the organic acids.

Palm

cocoanut

oil,

tallow and lard produce white soaps. In the yellow varieties these fats are mixed with rosin, cotton-seed oil, bone grease, " " Castile etc. Olive oil is used in making soap.

Amines are composed of carbon, and They may be looked upon nitrogen. hydrogen, with its ammonia as hydrogen replaced by organic radicals (cf. 527). Methylamine (CH 3NH2 ) and
541. Amines.

498
ethylamine

SOME CARBON COMPOUNDS.


(C 2

H NH

monia.
with

They
is

are gases much 5 2) are very soluble in water


salts.

like amand unite

acids,

forming

The most important

This is aniline (phenylamine), C 6 5 2 a colorless liquid made by reducing nitrobenzene.

amine

H NH
2
2

C H N0 +3
6 5 2

C H NH +2 H 0.
6
6

The nitrobenzene

is

reduced by adding to
acid.
2.

it

tin

(or iron) aniline hydrochloride,

and hydrochloric

The
is

resulting

H NH
5

HC1,
(cf.

a white

solid

like

ammonium
is

decomposed
Aniline

It is 210). aniline. caustic by soda, liberating used in making aniline dyes and many

chloride

other organic substances.

Alkaloids are nitrogenous sub542. Alkaloids. stances occurring in plants and often used in medicine

because of their physiological effect. Chemically they resemble ammonia: they unite with acids to

form

salts,

and

their
2,

aqueous solutions are alkaline.


found
in the

Quinine,

C 2o H 24N 2

is

bark of cinchona

trees,

and

is

used to reduce fevers.

Morphine, CnHigNOs, which occurs with other alkaloids in is used to deaden pain. Opium is made by evaporating the sap of unripe poppies. Paregoric and laudanum are prepared from it.
opium,
Strychnine (C 2 iH 22

2)

and brucine (C^H^NoO^ occur


Its salt,

in

nux vomica.
Cocaine
is is

found in cocoa leaves.

CnH^NCV

HC1,

used by dentists and surgeons as a local anesthetic.

MANUFACTURE OF CANE SUGAR.


The'ine
(or
caffeine),

499

C 8HioN 4O

2 -f

H 0,
2

is

the active con-

stituent of tea
Nicotine, Ci

and

coffee.
,

Hi 4 N 2

occurs in tobacco as the malate.

Sugars, starch, and cellulose are 543. Sugars. the most important substances of the class of com-

pounds known as carbohydrates. The most common sugar is cane sugar, which is made from sugar cane and from beets. Its formula is C^H^On. Isomeric with it (cf. 220) are maltose (malt sugar) and lactose
(sugar of milk). When cane sugar is exposed to certain ferments, or heated with dilute acids, it is hydrolyzed according to the equation
:

CuHaOu+HsQ

C6H

12

+C H
6

12

6.

glucose

fructose

Maltose decomposes according to a similar equaLactose gives tion, but only glucose is formed. glucose and galactose. All sugars contain (OH) 527 and 530). groups, like alcohols (cf. Milk sugar is not so sweet as cane sugar. It forms hard, white crystals, and is used for prepared
foods

and homeopathic pellets. The lactic acid ferment decomposes it (cf. 538). Cane sugar melts at about 160 C. At about 200 it forms a brown substance called caramel, which is used as a coloring for foods and liquors.
544. Manufacture of Cane Sugar. or sucrose, is prepared from the cane

Cane sugar, by crushing it

500

SOME CARBON COMPOUNDS.


boiling the juice with lime.

and

The lime

clarifies

sugar solution is a until cooled evaporated sample begins to crystallize. The evaporation is then continued in " vacuum pans/' so that the water distills off at a temperature
the juice.

After filtration

the

below that at which


pressure
(cf.

it

would

boil

under atmospheric
of

340).

The

crystals

sugar

are

separated from the liquid (molasses) by rotating the mixture in funnel shaped sieves through which only the molasses can escape. Raw or brown sugar is thus obtained. The preparation of sugar from
beets takes place in a similar way. The second operation is the refining of
sugar. in hot water,

raw

In

this process the

raw sugar is dissolved

the solution is stirred by blowing air through it, and coagulating substances are added to collect the Animal charcoal is used to make the impurities.
is

The resulting syrup 275). (cf. then concentrated in vacuum pans and left in tanks until it crystallizes. Finally the crystals of
solution colorless

sugar are separated from the adhering syrup in centrifugal apparatus and dried carefully for the

market.

545. Glucose and Fructose. Glucose, also called dextrose and grape sugar,
crystalline
solid
less

Hi2O 6 ,

is

a white,

melts at about 150

C.

sweet than cane sugar. It Glucose is found in grapes,


It occurs in the seeds,

and, therefore, in raisins.

GLUCOSIDES.
roots, leaves,

501

and blossoms

of plants,

and

is

formed

of sucrose, maltose, and lactose. Glucose reduces alkaline copper solution (Fehling's

by the hydrolysis

solution) giving cuprous oxide (cf. 459). Fructose (levulose or fruit sugar) is isomeric with It is a white solid, melting at 107-109, glucose.

and

is

almost as sweet as sucrose.

Both glucose and

fructose are fermentable.


Commercial glucose is made by heating starch with dilute sulphuric acid. This hydrolyzes the starch, giving several intermediate products, and finally glucose. The part that crystal" lizes out is called grape sugar," while the colorless syrup is " " " " " called or Glucose is used in glucose mixing syrup."
the preparation of
jellies,

candy, and syrups.

546. Glucosides.

sugar glucose

is

While in cane sugar and milk combined with fructose and galactose,

respectively, in

many

other natural compounds


derivatives.

it is

combined
called

with

benzene

These

are

glucosides.

Amygdalin,
2

the

tannins,

and

indican are examples.

Amygdalin,

and

in the kernels of

C oH 7NOn, is many
2

cherries,

dilute acids

and plums. decompose

found in bitter almonds fruits, such as peaches, The ferment emulsin and
into glucose, prussic acid,

it

and benzaldehyde.
C2oH 27 NOn+2

>

C6H

12

0+HCN+C6H CHO.
5

The

Tannins are found in the bark and leaves of many plants. chief sources are hemlock and oak bark, but they occur

502
also in tea,
glucosides.

SOME CARBON COMPOUNDS.


sumach,
gall nuts, etc.

Not
by

all of

the tannins are

The tannins

are characterized

their ability to convert

fresh skin into leather

and by

their forming black, green, or

blue solutions or precipitates with iron salts. They are therefore used extensively in tanning and in making inks. They are also used as mordants in dyeing (cf. 477).

The most important acids found in the tannins are gallic (C7H 6 5 ) and tannic acid (tannin), Ci 4 Hio0 9 Indican, C 26H 3 iNOi7, occurs in certain plants. When fermented, or when boiled with dilute acids, it breaks down into a sugar and indigo blue, the well known dyestuff. Indigo has It is now prepared synthetically in the formula Ci6 HioN 2 2
acid
.

large quantities.

found in grains, potaIt is made from maize and potatoes, and fruits. toes by reducing them to powdered form, adding water, and separating the starch, which is practically insoluble, from the gluten, oil, and cellulose with which it is mixed.
547. Starch.

Starch

is

ance.

Starch consists of small grains of varied appearHot water causes the grains to swell and burst.
7

The

resulting starch paste, suspended in water, is " called starch solution.' Starch is used in foods, " in making cloth, paper, and glucose, and for starch" clothes. of The formula starch is Hi 5 )n ing (C 6 0. The value of n is not known. 2

+H

Dextrin
is

is

formed from starch by the action

of

dilute acids.

The

sticky solution (impure dextrin)

used for mucilage.

CELLULOSE.
Bread
is

503

by the fermenting action of yeast. 70%) with about 15% each of water and gluten, besides small amounts of salts and dextrin. When flour, water (or milk), and yeast are mixed into a dough and set in a warm place, the yeast changes sugar
flour

made from

Wheat

flour consists largely of starch (about

(present as such, or produced from the starch) into alcohol " rises." In baking, the yeast dioxide, and the bread is killed; water, carbon dioxide, and alcohol escape, and the

and carbon

starch on the outside of the bread

is

partly changed to dextrin,

forming the crust.

548. Cellulose (C 6

H O )x.
10
5

Cellulose

is

the basis

forms the walls of plant and cells. paper are almost wholly Cotton, linen, Swedish filter paper is a purified form. cellulose. Cellulose is an amorphous, white substance insoluble When treated with concentrated in most solvents. and then with water it breaks down acid sulphuric Like alcohols, cellulose reacts with into glucose. The nitric acid esters were acids to form esters.
of vegetable tissue, since it

mentioned
solved
in

in

232.

Collodion

is

nitrocellulose dis-

alcohol

and

ether.

When

the solvent

evaporates it Collodion can thus be used to protect wounds and to attach silver salts to photographic plates (cf. 466).
Paper
1.
is

leaves a thin film of nitrocellulose.

made from
:

rags,

wood, or straw.

The

process con-

sists of several stages

Reducing the raw material to pulp and drying and pressing


filling ")

the pulp.
2. Mixing the pulp with clay or gypsum (" the paper a close texture.

to give

504
3.

SOME CARBON COMPOUNDS.


"
Sizing

"

pulp that

is

to be converted into printing or


Gelatin, rosin,

writing paper, so that the ink will not spread. or alum is used for this.
4. Polishing

the paper
of

The conversion

by passing it between rollers. wood into pulp is accomplished by

first

reducing it to chips and then heating the chips, under pressure, with sodium hydroxide or calcium acid sulphite (" bisulphite ";
cf.

259).

sized;

Newspaper and wrapping paper are generally unblotting and tissue papers are neither sized nor filled.

549. Phenol

and
a

its

Derivatives.
is

Phenol,

or
(cf.

hydroxybenzene,
297).
It
is

CeHsOH,

found in coal tar

white, crystalline, low-melting Its solid, which burns the skin and is poisonous. is as a solution used disinfectant. Phenol aqueous
reacts with alkalies to give salts; called carbolic acid.
Salicylic Acid.
is

it

is

sometimes

the sodium salt of phenol treated with carbon dioxide at 120, under pres-

When

sure, the

two unite to give sodium


This
Its
oil of
is

salicylate,

H OH.
4
3,

COONa.
is

used in medicine. Salicylic acid a white solid melting at 156 and used as a premethyl
ester,

servative.

C 6H OHCOOCH
4

is

present in

wintergreen.

Picric Acid, or trinitrophenol,

(NO )3OH,
2

is

made from phenol and fuming

nitric acid.

It is a

yellow, soluble solid used as a dye. picrates are used in making explosives.

Some

of the

Hydroquinone,

(OH) 3

are di-

and pyrogallic acid, 6 H 4 (OH) 2 and tri-hydroxybenzene, respec,

PHENOL AND ITS DERIVATIVES.


lively.

505

are soluble, white solids. Both are and are used as reducing agents developers in pho-

They
(cf.

tography

pyrogallol) is used in gas analysis.

466). Pyrogallic acid (also called to absorb uncombined oxygen

APPENDIX.

THE METRIC SYSTEM.


1.

Length.

The

unit of length

is

the meter (39.37

in.).

10 millimeters (mm.) TO centimeters

10 decimeters
1,000 meters

=1 centimeter (cm.). =1 decimeter (dm.). = 1 meter (m.). = 1 kilometer (km.).

Note that the


"
dollar;

"
prefix

centi-

"

means

means
2.

0.1, as

dime =0.1

dollar.

" means 0.001, as mill= 0.001 " " cent = Q.Ql dollar; as deci0.01, " "
milli-

Kilo-

means

1,000.

Square Measure, or Area.


100 square millimeters (sq. mm.) 100 square centimeters 100 square decimeters

= 1 sq. centimeter (sq. cm.) = 1 sq. decimeter (sq. dm.). = 1 sq. meter (sq. m.).
is

Cubic Measure, oc Volume. The unit of volume liter, which is 1 cu. dm., or 1,000 c.c.
1,000 cubic millimeters (cu. 1,000 cubic centimeters
l^cubic decimeter

the

mm.) = 1

cubic centimeter

(c.c.).

1 cubic decimeter (cu. dm.),

10

liters

10 dekaliters

10 hectoliters
4.

=1 =1 =1 =1

liter (1.)--

dekaliter (dl).
hectoliter (hi.).
kiloliter (kl.).
.

Weight.

The gram

1 liter of

is the weight of 1 c.c. water at 4 C.; water at 4 C. weighs 1 kilogram.

10 milligrams (mg.) 10 centigrams 10 decigrams


1,000 grams

= l centigram (eg.). =1 decigram (dg.). = 1 gram (g^. = 1 kilogram (kg.).


i

ii

APPENDIX.

TABLE OF EQUIVALENTS.
1.

Length.
1
1 1 1 1

centimeter = 0.3937

in.

meter
kilometer
inch
foot

= 39.37 = 1,000

in.

= 3.28

ft.

m. = 0.6214

mile.

1
2.

mile

=2.54 cm. = 0.3048m. =1.6094 km.

Area.

cm. =0.155 sq. in. = 10.764 sq. ft. = 1.196 sq. yd. m. 100 m. square =10, 000 sq. m. = l hectare = 2.47 1 sq. km. =0.385 sq. mile.
1 sq.

1 sq.

acres,

3.

Volume.
1 cu.
1 cu.

cm.

= 0.061

cu. in.
cu.
ft.

m. =35.315

1 liter

= 1,000

cu.

cm.

= 1.0567

qt. (U. S.)

4.

Weight.
1

gram
kilogram metric ton
or net ton
or gross ton

1
1

= 15.4324 grains. = 1 ,000 grams = 2.2046 Ibs. = 1,000 kg. = 2,204.6 Ibs.
=2,000
Ibs. Ibs.

1 short, 1 long, 1

= 2,240

grain

1 1

=0.0648 gram. ounce (avoirdupois) = 28.35 grams. ounce (troy) =31.1 grams.

APPENDIX.

Ill

TABLE OF ATOMIC WEIGHTS AND SPECIFIC HEATS.

IV

APPENDIX.
Continued.

TABLE OF ATOMIC WEIGHTS AND SPECIFIC HEATS.

APPENDIX.
TENSION OF AQUEOUS VAPOR IN MM. OF MERCURY (REGNAULT).
TEMP.

VI

APPENDIX.

HEAT OF FORMATION AND HEAT OF SOLUTION IN KILOGRAM CENTIGRADE UNITS (1,000 CALORIES).
NAME.

APPENDIX.

Vll

sapiqdjng

sa^qdjng

sa^eqdsoqj
sapixQ

sapipoj

saprxojpXjj

sapuonu
sapitreXoo-uaj

sapuojqo

gapnnoig

s*
.sp
1-9

Vlll

APPENDIX,

ide.

Hydrox-

35
p

APPENDIX.
o
tN. lft TO
fr.

IX

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SB?

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rrf

t^

p U
JJ3

cj

*>

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i

^SSSSSSSSJSsiiiiid

&
t^

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gp-i^g^^s^^ * g
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fiS

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X
LIST OF

APPENDIX.

THE METALS IN THE ORDER OF DECREASING SOLUTION TENSION.


Lead.
Metals.

The Alkali Metals. The Alkaline-Earth


Magnesium. Aluminum.
Manganese.
Zinc.

Hydrogen.
Bismuth.

Antimony.
Copper.
Arsenic.

Cadmium.
Iron.

Mercury.
Silver.

Cobalt.
Nickel.

Palladium.

Platinum.
Gold.
first

Tin.

The metals appearing

in the table can replace those that

follow, in the solutions of their salts.

CRYSTAL FORMS.
Crystals are the forms assumed by most solid substances. They are bounded by plane faces, which express outwardly a Six systems of regular arrangement of the molecules within.
crystals are distinguished:
1.

2.

Isometric, or regular. Quadratic, or tetragonal.

5.

Monoclinic,
metric.

or

monosym-

3.

4.

6. Triclinic, or asymmetric. Hexagonal. Orthorhombic, or rhombic.

FIG. A.

APPENDIX.
This classification
(in
is

XI

one
1.

case, four) lines, or

based upon the relations between three axes, which determine the positions

of the crystal faces.

Isometric System.

right angles,

and

are equal.

In this system the three axes are at Fig. A shows three isometric solids:

the cube, the octahedron, and the dodekahedron. Salt, alum, potassium iodide, galena, iron pyrites, and the diamond crystallize
in this system.

FIG. B.

2.

(Fig.

Quadratic System. The crystals of the quadratic system B) have three axes at right angles, but only two are of

equal length.
3. Hexagonal System. This system has four axes, three of them equal and in the same horizontal plane. Fig. C gives two illustrations. The three equal axes

bisect one another so as to

form 60

perpendicular to the plane of the other three, at the point of then' intersection. The
angles.

The

fourth axis

is

prism,

pyramid, and rhombohedron FIG. C. Substances belong to this system. crystallizing in the forms of the system are quartz,

ice,

and limestone.
4.

Rhombic System. Here

there are three axes,

all

at right angles, but no two are of equal length. Sulphur (Fig. 55), potassium nitrate (Fig. D), and the garnet
FIG. D.

crystallize in this system.

Xll

APPENDIX.
5. Monoclinic System. In this system there are three axes of unequal Each one bisects the other length. two, but only two of the axes are at

right angles (Fig.


clinic sulphur,

E)

Gypsum, mono2),

rock candy (Fig. E,


salt

Fro. E.

and

Glauber's

belong

to

this

system.
6.

Triclinic

clinic

System. Crystals of the trisystem have three axes of unequal

length,

and the

intersecting angles

are

all

Blue vitriol (Fig. F) and potassium dichromate crystals belong in


this system.
Fio. F.

oblique and unequal.

CORRECTION OF BAROMETER READING FOR TEMPERATURE.


To
(cf.

find the height


43,

text)

subtract the

which the barometer would have at C. " " Correction from the proper

reading of the barometer, in millimeters.

TEMPERATURE,
C.

APPENDIX.
into
its

Xlll

primary colors,

violet,

indigo, blue, green, yellow, orange,


violet light

and

red

(VIBGYOR). The waves producing

are the

The prism those producing red light, the longest. separates white light into colored rays because it bends, or refracts, the short waves more than it does those of greater
shortest,

length.
least.

Hence the violet rays are bent most, and the red rays After refraction, the beam of white light appears as a
colored images of the
slit

band, made up of
This band
is

placed side

by

side.

called a spectrum.
(Fig. G) is

The spectroscope
and Kirchhoff,

an apparatus devised by Bunsen


It consists of

in 1859, for studying spectra. prism (P) contained in the central part of the instrument (when in
use, this is covered)

and the three

tubes (A), (B), and (C). (A) contains lenses, which gather the light rays admitted through the

narrow

slit

(S)

and

direct

them

The observer to the prism (P). looks through the telescope (C). This magnifies the images of
the
slit

which

together

make

up

tube spectrum. or (B) contains a scale, which is illuminated by a candle other light. The spectrum and the magnified scale are seen
the

The

FIG. G.

be designated together, and the parts of the spectrum can thus scale. on the their positions by 419 and 420) that volatile potassium We have seen (cf. compounds give a violet color to the Bunsen flame, while sodium in a compounds make it yellow. When a sodium salt is placed Bunsen flame, before the slit of an ordinary spectroscope, the
yellow color

This is located confined to a single bright line. of the spectrum the forms in what at a definite place yellow part two red other the on gives hand, of white Potassium,
is

light.

APPENDIX.
one end of the spectrum, and a violet line at the other of these elements can thus be readily detected in a mixture. The same is true of other mixtures of elements: each
lines at

end.

Both

element has

its

own

lines,

in definite parts of the spectrum,


It has

regardless of the presence of others.

been found that

(joir

io

uo o of a gram of sodium can be detected by the

spectroscope.

The light given off by incandescent solids or liquids (cf. 302) produces a continuous spectrum, but the spectra of incandescent gases, like the vapors of sodium and potassium, are bright-line
spectra they are made up of bright, colored lines separated by dark spaces. When light from an incandescent solid substance
:

passes through the vapor of the


call
is

same substance, the

lines are

in their proper places in the spectrum, but they are dark.

We

such spectra absorption spectra. The spectrum of sunlight a continuous spectrum crossed by dark lines (" Fraunhofer's

lines ")

which are in the positions belonging to many well

known

terrestrial elements.

of our earth are also present in the sun.

Hence we argue that these elements The light from the solid

or liquid substances in the photosphere of the sum passes through the vapors of the same substances in the sun's atmosphere; hence

an absorption spectrum is produced. The light of many stars has properties like those of sunlight. The Bunsen flame is not hot enough to volatilize the salts

many metals; for these the electric arc may be used. This produces a spark spectrum. The spectrum of a gas is obtained by sealing the gas in a glass tube provided with electrodes, reducing the pressure with a vacuum pump, and passing an electric discharge through the gas.

of

INDEX.
[Numbers denote
Absolute alcohol
temperature
zero
pages.]

....
.

Acetaldehyde
Acetates Acetic acid

488 31 31 490 494

Acid, hydrocyanic
hydrofluoric

271

hydrosulphuric

hypobromous
hypochlorous hyponitrous hype-phosphorous
iodic
lactic

295 232 308


104,304 216 326 308 495 496 328 475 142, 202 208 211

....

Acetone
Acetylene
series

200,256,491,493 492
271,273,275,283 481
147

....
salts

Acid and normal


anhydrides
radical
salts

malic

143 145
147

metaphosphoric metastannic
nitric
nitric,

acetic

arsenic

arsenious

antimonious
benzoic
boric

bromic
butyric
capric

caproic carbolic

carbonic
chloric

chlorous
chlorplatinic
citric
fluosilicic

200,256,491,493 336 334 340 495 363 308 495,497 497 497 276,504 263 306 306 477 496 358
269,494 502 404 301 298 109, 110

fuming

nitrous
oleic

oxalic

palmitic

........
.
.

perbromic
perchloric
*.

perchromic
periodic

phosphoric phosphorous
picric

plumbic
propionic
prussic

pyrogallic

pyroligneous

formic
gallic

pyrophosphoric pyrosulphuric
salicylic
silicic

hydrazoic hydriodic

hydrobromic
hydrochloric

stannic
stearic

495,497 495 495, 497 308 307 466 309 327 326 504 471 495 271 504 493 328 240 504 360 475

495,497

XVI
Acid, sulphostannic
sulphuric

INDEX.
475
142, 241

Aluminum,

carbonate and

sul-

sulphurous tannic
tartaric

thiosulphuric
uric

Acidity and basicity Acids, action on bases action with oxides


active

....

239 502 495 249 479 149 143, 145 146 160
151
151

phide) hydroxide, uses occurrence and preparation


of

434 432

oxide and hydroxide


properties of
salts

uses of

Alums

.'

428,429 431 429 433 430 433


431

Alundum

binary

nomenclature of
organic
polysilicic

properties of
see

151,493 360 113,142


names.
160
151

389 Amalgam, ammonium Amalgamation process for silver, 420 112,368,412 Amalgams 497 Amines Ammonia, action of chlorine

under

specific

on
action with metals

105, 188, 193

strong and weak

ternary

Acker process
Agent, drying
Air

379 41,108,184

a refrigerating agent chemical properties of commercial sources of


composition of

.... ....
.
.

188 187 188


192

184, 185

and chemical change


. .

...
.

12

Air, a physical mixture


liquefaction of
liquid, properties of

85, 181

from illuminating gas manufacture

177 178
.

276
206. 207

from

nitric acid

proportion of oxygen in

16,

179

Alabaster

396
171

Albumins
Alcohol, absolute

laboratory methods of preparation 183 * 186, 187 liquefaction of


.
.

amyl
butyl
ethyl

.'

methyl
propyl

Alcohols

Aldehydes
Alizarin
Alkalies, defined Alkali metals

488 488 488 196,260,486,487 485,487 488 485 490 484


144,374 369,374 392 498

occurrence of
physical properties of

183

....
. .
.

185

process of making soda

380
4

reagent
synthesis of

Ammonium
amalgam compounds
hydroxide
.

192 190

389
.

189,190,389,390
of
. .

compounds, dissociation
. .

191

Alkaline earth metals Alkaloids

Allotropism
Alloys

Aluminates

Aluminum and its


bronze carbide

228,229,252 368,408 431 428 compounds 417


.

183,189 252, 253, 254 Amorphous carbon 74 Amorphous substances 501 Amygdalin 350 Analogues of an element 50 Analysis of water

....
. .

volumetric, use of permanganate in 458

.484

Anhydride of acid and base 211, Anhydrides


.

143, 146 237, 240

INDEX.
75 498 Animal charcoal and boneblack 257 158 Anion 445 Annealing and tempering steel 362 glass 483 Anthracene 334 Antidote for arsenic 337 Antimony 341 black 338 chemical properties 340 compounds 338 physical properties 337 preparation 341 trisulphide 341 uses of 398 Apatite

XV11
81,83, 123, 158

Anhydrous substance
Aniline

Atoms Atoms and molecules


number
of,
.

83,84
molecules
of

in
.

elements

123,313,321,377
. . .

A vogadro's hypothesis
Bacteria

.122
172 261

Baking powders
Balanced,
tions

........
reac-

or

equilibrium,

.........

Barium compounds Barium chloride

192,219,221 401

401,404 401 hydroxide 402 peroxide 18 peroxide, a source of oxygen Barometer 28 Barometric reading, correct 34
.
.

Aquaregia
Argol
family

101,207 384
172,

Baryta water Base bullion

144,401 421
.

Arsenates

XV111
Blowpipe, mouth oxyhydrogen Blueprints

INDEX.
....
.

286

Blue vitriol

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


of solutions,

Calcium, sulphate
sulphide

39b
40(>

45, 284

425,451 75,418

Calculations from equations from formulas

Boiling-point
of water

Calomel
Calorie

127, 128, 155

Bone-ash Bone-black and animal charcoal Borax and borax bead ..... Bordeaux mixture ......
Boric acid
tion

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


.

..........

60 319 257 364 418 363

Candle flame
power

Cane sugar Caramel


44 Carats fine" Carbides Carbohydrates Carbolic acid
.

Boron, occurrence and prepara-

94 92 411 45, 159, 290 282 285 499 499 427 273 499
.

........ 362,363 .......... 363 oxide ..... ....... 364 properties of ........ 363
nitride

Carbon
amorphous
coke and gas reduction by

276,504 252 253, 254


271

Carbon and hydrogen compounds,

Boyle's or Mariotte' slaw

32 417 Brass. 503 Bread 228 Brimstone 473 Britannia metal 308 Bromicacid 297 Bromine 307 oxyhydrogen compounds of 297 preparation of 298 properties of 417 Bronze 498 Brucine 283 Bunsen burner 285 Burner, Welsbach 15 Burning in air Butane 275, 481 481 Butylene

...

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


.

256 257 263

Carbonates
identification of

....

natural

Carbon dioxide
chemical properties of in the atmosphere occurrence of other sources of
physical properties of

....

264,265 267 257 259


174 257 260 258 258 262 236

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


.

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

*
. .
.

preparation
relation of, to
life

Carbon disulphide Carbon monoxide, formation


laboratory method
properties of reduces iron ore

of,

268, 275

Cadmium
Caffeine

Calcium
carbide

409 499 393

Carbonic acid Carbonic anhydride


Carbonization, natural;
coal
. .

carbonate
chloride

.......... ........ hydroxide ....... 144,395 46 light ........... oxide ........... 393 phosphate ......... 398 silicate .......... 400
cyanamide

273,400 .. 396 395 400

268 269 439 263 263 254

Carbon tetrachloride

Carborundum
Cast-iron Castner's process
Catalysis Catalytic agent

236,492 359 440


:

376,378
18

Caustic potash Caustic soda


.

18,51,106 385 378


.

INDEX.
Cavendish,
Celluloid Cellulose
Sir

XIX

Henry

...

50, 173

Cement and mortar


hydraulic

....
. .

Portland

210,211 210,503 398, 399 399 399

Chlorine dioxide and tetroxide, 303 Chlorine hydrate 102 Chlorine monoxide 303

Chlormethane Chloroform
Chlorophyll Chlorous acid Chlorplatinic acid

Cementation process Cerium dioxide Chalk

Chamber crystals
Change, chemical

442,445 285,292 396 244


2
22,

492 492 262 306 477


462, 463, 464, 465

Chromates and dichromates,

chemical, and energy changes,

Chrome-alum Chromic anhydride


Chromite Chromites

289
2

462 462 460

physical

Changes, quantitative character


18,55 Charcoal, animal, and bone-black, 257 257 reduction by
of chemical

wood
Charles' law

Charring
changes

254,255 30,31 254


289
quantitative
18,

Chemical changes and energy Chemical changes,


character of

460,461 469 460 ffg. compounds oxides and hydroxides 460 trioxide 462 Chromous and chromic salts 461 361 Clay Closed and open chains 482 Coagulation, purification by, 58, 432 Coal 254

Chromium

....
. .

....

55

Chemistry and
between
definition of

physics, relation

9
1

importance of Chili saltpeter

9,

10

China
Chloral Chlorates and Chlorides
insoluble

202,209,383 434 492 306 chloric acid 114


. .

....

Coal gas 269,275 Coals and wood, composition 255 Coal tar 257,276 Cobalt and its compounds .... 452 Cocaine 498 427 Coin gold 422 Coin silver
.

Coke
Collodion

114
of,

Combination Combining proportions Combustion


heat of
in air in chlorine

256,276 210,503 78
.

55, 63

15,

Chlorine, action

on ammonia,
105, 188, 193

21,22 ffg. 22.289 21,24


15, 21,

and bleaching and hydrogen, union and hydrocarbons

105
of
.

chemical properties of occurrence of


liquefaction of

....

103,111 105 103

products of rapid reversed

103 24 21

98
102

spontaneous
supporter of

25 25

preparation of
properties of uses of
.

98, 99, 100, 101

102,103,104,105

.105
102

water

21,25 439 310 halogens 345 of the nitrogen group 374 Comparison of the alkali metals

Commercial iron Comparison of the

....
.

XX
Comparison
metals
of the

INDEX.
alkali-earth

Cyanogen
392
7,9

270
24
.

Compounds

binary nomenclature
ternary

95, 1.51.
ot

95,

96

Davy's safety lamp Deacon's process for chlorine Decantation and nitration

101

8
21

95, 151

Concrete

399

Decay of wood Decomposition


heat of

Conductance of solutions .... 156 Conservation of matter .... 79 Constant Proportions, law of 55
. .

Constitutional formulas Contact action

199,

481 18
18 241

Contact agent Contact process


Converter, Bessemer

78 290 76 Decrepitation Definite proportions 9,55,63 80 explained by atomic theory 22 Deflagration Dehydrating or drying agents,
.
. .

41,76
76 Deliquescence 4 Density methods of vapor 125 Victor Meyer's method 125 Developing, photographic .... 423
.

....

Copper
alloys

compounds
etc., relation

to alkali

415,443 414 ' 417 417,418 414 metals


.

metallurgy of
native
ores
. .
.

415,416 414 414

Dewar bulbs
Dew-point
Dextrin

179

416,417 properties and uses sulphate use in making hydrogen

Diamond
Diatoms Dichlormethane Dichromates and chromates
Diffusion, explanation of

Copper-plating Coral Correction of the barometric 34 reading 411 Corrosive sublimate

39 419 267

....
. . .

hydrogen Dioxides and peroxides


Dissociation by heat
of

of

175 502 252 356 492 462 85 42

.317 Disodium hydrogen phosphate, 328

Corundum
Crayon

431 396

.... 62, 225 in solution, ionization .... 155


ammonium compounds
.

Cream of tartar
Critical

261,389
. .

.191
331

temperature defined
.

177

of arsenic molecules

Crucible process for steel


Cryolite Crystallization from fusion water of

442,444 295

of hydriodic acid .......... 302 of hydrobromic acid 299

73 74 75 73 Crystals systems of Appendix x 92 Crystal-water, how represented 418 Cupric compounds 270 cyanide 418 Cuprous compounds Cyanide process of extracting 426 gold
.

of iodine
of nitrogen tetroxide
. . .

301

.213
62,

of

steam

Distillation
destructive Distilling at reduced pressure

Disulphuric acid

Dolomite Double cyanides

284 58 255 315 240 267

......

422*426
79, 155
,

decomposition Drafts, combustion in

24

INDEX.
Drying agent
41,76,108,184 calcium chloride 41,76 calcium oxide 77, 184 386 potassium carbonate sodium hydroxide 184

XXI
of

....

Elements, number
molecule of

atoms

in

122, 123

....

periodic table of prediction of unknown

properties of ,

determined

346 352 350


431 501

Dulong and

sulphuric acid Peril's rule

54,98

....

Emery
Emulsin Endothermic Energy
reaction
5, 9,

Dust, atmospheric Dyes, classes of

136 176

290
107, 289

Dynamite
Earthenware
Effervescence Efflorescence

433 210 435 74 76

changes accompany chemical changes 9,21,22,289 289 potential, of elements

....

Equation,
anced
ionic

equilibrium

or

bal-

157, 192, 220

163 Electric charges Electric conductance of solu156 tions


Electric furnaces,
287, 319,

222 volumetric meaning of 195 Equations and molecular formulas 195

....

357, 368,

400, .431,

and symbols, meaning of


balancing of

quantitative

88,94
92, 195

442
Electric steel

Electro-chemical equivalents
Electrolysis
of hydrochloric acid
.
.

442 166
164

complete
partial

100,222 99
of
.

101,111 of sodium chloride 102,379 of water 47,50 429 preparation of aluminum by 393 preparation of calcium by 385 preparation of potassium by 376 preparation of sodium by
. . .
.

symbolic the result

Equilibrium
chemical
ionic

87,91 experiment ... 91 62,192,219,221 219,221,223 222


.
.

or balanced equation

.157
219

physical unstable, of

compounds with
.

preparation

of

sodium

hy-

negative heat of formation

291 166 150

droxideby
Electrolytes
,

378
156
.
.

Equivalents, electro-chemical

Equivalent solutions
weights Esters

Electromotive series
Electroplating Electrons
.

161,370
404 419 350
7
65,

....
. .

389, 419, 422

64,135 496

<

Etching

of glass

Electrotype plates

Ethane
Ethers Ethyl acetate amine
ether

Element, analogues of an Elements, abundance of


atomic weights of
classes of

....
.

133
6

296,362 271,272,275,481 489 496 498

hydrogen sulphate
equivalent weights of heterologous
.

65, 138
.

homologous
list

350 346

Ethylene Ethylene series

Eudiometer
Evaporation

of

7,

Appendix iii
122,195

molecules of

Exothermic reactions

489,490 490 271,272,275 481 52 221 290


.

XX11
Factors and products Factors of solubility
.

INDEX.
. .

Family, argon
calcium

halogen
nitrogen

INDEX.
Gases and vapors
Gases, diffusion of measurement of
molecular weights of
pressure of solution of in liquids
,

XX111
294 309 303
304 397

177
42, 85

28

....
....

123

28
71
121

Halogens Halogen family Halogen -oxygen compounds comHalogen oxyhydrogen pounds Hardness of water 59,
.

Gay-Lussac'slaw
Gasoline Generating flask Generator, Kipp's

485 39 40
pre-

Heat, dissociation by 62, 191, 213 of formation and decomposition 289,290,305


. .

of
,

Germanium,
dicted

properties

of neutralization

formation evolved in stages, 313 159 287 173 180 72 350 481 346 480 8

German silver
Glass
color of

352 417

sources of

cut

110,296,361 362 362

Helium Hempel pipette


Henry's law Heterologous elements

.... ....

etching of
pressed

Glauber's salt

Glucinum
Glucose Glucosides Glycerine

296,362 362 384 392

Hexane Homologous elements Homologous series Hornblende


Hydrate
Hydration, water of Hydraulic cement
mining
of gold

200,500
501

Gold
fineness, in carats

and uses of .... Gram-atomic weight Gram-molecular weight,


properties

488 425 427 426 88

75,245 75 399 425


301,302 303 298
. .

Hydriodic acid
powerful reducing agent Hydrobromic acid
.

Hydrocarbons
.

271,480
. .

89, 125 156, 196

Gram-molecular volume
.

126, 196
.

Granite 8,428 " Granite ironware " 361 200, 500 Grape-sugar Graphic, or structural, formi ilas,
.
. . .

Hydrochloric acid, commercial method of preparation 109 common method 108


electrolysis of

occurrence of
properties synthesis of

101,111 108 110, 113

199, 481

.111
.
.

Graphite

253, 439
. .

Greens, arsenic

Green

vitriol
.

Gun cotton
metal
.

335 450 210 417

volumetric composition of Hydrocyanic acid Hydrofluoric acid

Ill

271

295
340*
' .

Hydrogen and
antimonide
arsenide

chlorine, union, 103, 111

*
.

powder

Gypsum
Haematite
.

20,22 211,387 396


.

chemical properties
chloride
diffusion of

332 43

.436
.

294 Halides Hall's process for making alu428 minum


. .

108,110,113 42 methods of preparation ... 38 43 occlusion of occurrence of 38


.

XXIV
Hydrogen, peroxide
peroxide, test for

INDEX.
....
314, 315

peroxide, composition of

...

phosphide
physical properties of

....
of,

317 316 323 42

Indican Indigo

Ink

preparation and properties


purification of

38,42 40 46 reducing power of 357 silicide 232, 233, 246, 276 sulphide 42 transpiration of union with oxygen 44, 45 48 uses of

....

....

sympathetic lodates lodicacid Iodine 300,301 Iodine oxyhydrogen compounds, 304, 308 301 Iodine pentoxide 493 lodoform 162 Ionic equation 222 equilibrium lonization 157,159

502 502 450 452 308 308

Hydrogen-carbon

compounds,
271, 480

lonogen
Ions
oxidation and reduction of
.
.

157
157

Hydrolysis .... 166,224,380,398 224 and mass action of aluminum carbonate and 434 sulphide 403 of magnesium carbonate 380 of soap
.

162

Hydroquinone
Hydrosulphides Hydrosulphuric acid Hydroxides action of metals upon Hydroxyl

424, 504

234 232

....

63,144 64

Hydroxylamine
Hygroscopic

"Hypo"
Hypobromites
Hypochlorites

145,158 206 76 250 308 305


104,304 216 217 326 122 80

Hypochlorous acid Hyponitrous acid


anhydride

....

436 439 440 cast 449 Iron chlorides 439 commercial compounds, ferrous and ferric, 448 408 galvanized 441 malleable 436 occurrence and metallurgy 448 oxides and hydroxides 446, 447 properties of 231,436 pyrites 450 sulphates 449 sulphides 451 thiocyanates 440 wrought 200 Isomers

Iron

carbide

....

Hypophosphorous acid
Hypothesis, Avogadro's
atomic

.... ....

Iceland spar Ignition temperature Illuminating gas 274, comparison of the two kinds
.

distillation of coal

water gas process

Incandescence

267 23 276 278 275 278 284

Kaolin Kation Kerosene Kiln Kindling temperature

361 158

485 394 23
172

Krypton
Lactose

Lampblack
Latent heat
of
.

499 255
water
.

61

Laudanum

498

INDEX.
Lavoisier
13

XXV
431 267

Magnalium
Magnesite Magnetite

Law, Boyle'a or Marietta's


Charles'
of
.

...
.

32, 33

of conservation of

matter

30,31 79
.

Magnesium
carbonate

448 402
267 402 402 358 385 499

definite

proportions
proportions

by
55

weight
of
definite

compounds
oxide
silicide

by
121
121

of of

volume Gay-Lussac

sulphate

Henry
work

of maximum

72 292
79, 80, 81

Maltose

of multiple proportions,

Manganates Manganese
dioxide

Laws of osmotic pressure


of definite

....
vol.
.

129
121

and multiple umes Lead and its compounds

compounds and hydrogen peroxide


.
.

456,457 455 455, 456


317
19

occurrence, preparation oxides, nitrate and acetate


.

properties
sulphate,
chloride,

467 ffg. 467 469 468


. .

dioxide a source of oxygen dioxide, action on potassium


chlorate
dioxide, to liberate chlorine
.

18
98, 99

and

car-

oxides

bonate
sulphide
tree

uses of

470 470 468 468

Manganites Marble
Mariotte's or Boyle's, law
.

455 456

Marl

267,398 32, 33 396


.

white

.470

Marsh gas
series

Le Blanc process

110,380 501 Levulose 262 Life, relation of carbon dioxide to Light, action on silver compounds, 424 485 Ligroin
.

Marsh's

test for antimony

for arsenic

271,489 480 340 332


. .

Lime
"air slaked"
light

77,393 395 46 77,395


144

Mass Mass action Matches


Matter
conservation of
physical states of

4 224 322
4

79
5

slaking

wafer

Maximum work, law of


Mercur-ammonium salts
Mercuric chloride
cyanide fulminate
iodide

....
.
.

292
411 270 412 412

Limestone
Liquefaction
of of air

267,396
177 186 178
85^

.411

ammonia
air, properties of
of

Liquid

....

Liquids, diffusion

Liquors

Lithium Litmus
Lodestone

488 375
113

oxide

sulphide Mercurous chloride and oxide


iodide

Luminous flames Lunar caustic


Luster, metallic

448 281 423 366

14,410 411 411 412


.

Mercury
compounds Metaborates
.

14,409 411,412 ... 364

XXVI
Metal radical
type
. . .

INDEX.
190 343 341 343 366 366

Wood's
Metallic luster Metalloids Metals, abundance of
.
. .

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


''.".'"'.^
.

Molecules of elements and of 84, 123 compounds of elements, number of atoms


in

Mordant, aluminum compounds


Morley, Edward

Morphine
Mortar and cement
Multiple proportions, law
of,

alkali

alkaline-earth

and non-metals
base
classification of

compounds
heavy

of

extraction from ores

369,374 369,392 6, 366 370 368 371 367 366

122,123 432 55 498 398, 399


.

79, 80, 81

Multiple volumes Multiples of symbols and


mulas,

121
for.
.

how

represented
of

89

Naming

compound

two
of

ele-

hydroxides of
light

noble occurrence of oxides of


properties of

47,143,371 366 370 367

ments
different

95

compounds

same
96

two elements

....

46,48,146,371 6, 47, 366


12

rusting of

Metaphosphate bead Metaphosphoric acid

329
.
.

327,328
271 497 492

Methane Methylamine
Methyl
chloride

276,483 106,298,306 Natural families 346 Natural family of elements 309 Natural gas 485 Neon 172, 353 Neutralization .... 143, 145, 224 158, 224 explanation of
.
.
.

Naphthalene Nascent state

heat of
. . .

159

ether
nitrate

200,489 486

Mica Milk of lime


Milk sugar Minerals Mirrors

8,428 385,395 499 367


422,491 399 7, 8 73 126 150
. .

Mixed

salts
.
.

Mixtures and compounds


freezing

Nickel and its compounds .451 Nicotine 499 Niter 14, 210 Nitrate, manufacture of potassium 210 Nitrate beds 209 Nitrates and nitric acid, uses of 210 Nitrates 209,215 properties of .... 209,212,214
sources of

Molar weight
solution

209

Nitric acid
action on metals

Molecular formulas and equations, 195


theory
84,

....
.

85

and

nitrates, uses of

Molecular weight
boiling-point

123

commercial preparation

and freezingpoint methods .... 127, 128 125 vapor density methods
.
.

fuming
laboratory preparation of oxidation by
oxidizing agent

of gases

124

Molecules and atoms

...

83, 84, 123

preparation

142,202 205, 206 210 202 208 203 207 205, 207 203
.
. .

INDEX.
Nitric acid, preparation compared with that of hydrochloric acid, 204 properties of 142, 205 reduced by nascent hydrogen, 205, 207 Nitric anhydride 211 Nitric oxide 214 Nitrides 171,184 Nitrites 212

XXV11

Oxidation by bacteria .... 209 by chromates and dichromates, 465 by nitric acid 205,207 by permanganate 458 Oxides 19 of metals and non-metais 145
.
.

of

phosphorus with acids, action of with bases, action of

....

210,483,498 Nitrocellulose 210,503 Nitrogen 14,169,171,330 dioxide and tetroxide .... 213
family

Nitrobenzene

Oxidizing agent
bacteria

bromine
chlorine

325 146 146 20,46 21,209 298


.

104, 106

from

ammonium

nitrite

occurrence of of the air, a mixture 171 oxides 211,212,213,214,215 211 pentoxide


.

343,345 170 169


.

chromates and dichromates hydrogen peroxide


nitric acid

ozone

permanganate Oxidizing flame

preparation

of,

from

air

...

169

Oxygen acids of phosphorus

465 316 205,207 313 459 286 325


.

properties of trioxide

170

Nitroglycerine Nitrous acid


anhydride
oxide

211,212 210 211 211

chemical properties of determination of the proportion


of, in air

....

19

18,

occurrence of
physical properties of

15,

179 26

214,215,217
151

Nomenclature of acids
ofbases
of

compounds

of salts

Non-luminous flames Normal salts


solutions

153 95, 96 152 283 147


150,159'

19 preparation of 16, 17, 18 standard of atomic weight, 82, 124 standard of molecular weight, 124 uses of 26

.... ....

xy-hydrogen blowpipe
t>ne

45, 284

312,313

Paints, luminous

400
of

Occlusion of hydrogen Oil of wintergreen Oils and fats


Olein

....

43 504 497 497

Palladium, occlusion gen by Palmitin Paper


Paraffin

hydro-

43 497 503

Open hearth

process for steel,


442, 444 498 367 367 479 330
.

Opium
Ores
extraction of metals from

Paregoric Paris green Parke's process


lead

480,485 498 335


of

desilverizing

<

Partial pressure

Organic compounds

Peat

Orpiment Osmotic pressure


Oxidation

Pentane
Perchlorates Perchloric acid
.
.

129,130 20,21,205

421 35 254 481 307 307

XXV111
Perchromic acid
Periodic acid Periodic arrangement
.
. .

INDEX.
466 309
.

346 ffg. 353 conclusion 351 gaps in 349 regularities in 349 Periodic law 177 Permanent gases 456, 457, 458, 459 Permanganates 317 Peroxides and dioxides 314 Peroxide of hydrogen 484 Petroleum ... 485 ether T^r-r'
.

Plumbites and plumbates Pneumatic trough Polymers Poly methylene series


Polysilicic acids

...

471
17

199 481

360
384, 391
. .

.....

Poly sulphides
Porcelain-lined ware Porcelain, stoneware,
etc.
. . .

.361
.
.

....
'.

Portland cement Potash

'.

Potassium
bromide
carbonate
chlorate

434 399 330, 384 384


.
.

....

.387
267, 389

Phenol Phosphates, necessary


uses of

for plants,
.

Phosphide of hydrogen Phosphides Phosphine

....

Phosphonium salts
Phosphorescence Phosphoric acids
preparation of
salts of

276,504 329 329 , 323 324 323 324

chromate
cyanide dichromate
ferricyanide

ferrocyanide

hydrogen tartrate
hydroxide
in fertilizers

Phosphorous acid Phosphorus


molecular weight of
oxides

230,400 327 327 328 326 319 321


320,325 325 320
321

iodide
nitrate
nitrite

306,387 462 389 464 450 450 389 385 330 387

permanganate
silicate

sulphates

oxygen acids
properties of red

of

thiocyanate

210,388 389 456 ffg. 361 388 389

Photography Photometer

423,424 285
2 9

Physical changes Physics, relation between Chemistry and


Pig-iron Pins

437 473 279 Pintschgas 180 Pipette, Hempel 425 of Placer-mining gold Plants and oxygen 26 Plaster of Paris 396 Platinized asbestos 241 Platinum, occlusion of hydrogen, 43 occurrence and preparation 476 476 properties and uses
.

261 74 Precipitate Prediction of unknown elements, 352 28 Pressure and temperature osmotic 129, 130 35 partial relation to volume of gas 32, 33 standard 29, 36

Powders, baking

....
.
.

Priestley, Joseph Producer gas Products and factors

13

279,439 3,4 calculation of quantities of 63,88 275,481 Propane


.

Properties
of acids

1, 2,

effect of structure

on

....

317

ofbases
of salts

113,142 143
145,147

INDEX.
Proportions, definite
multiple
. .

XXIX
g
26
. .

....
. . .

Prussian blue
Prussic acid

... ... ...

Puddling process
Pyrites Pyrogallic acid (pyrogallol) Pyrolusite
.

53,55 79 450 271 441

Residue
Respiration Reverberatory furnace Reversed combustion Reversible reaction,
.

.421
25

231,436 180, 504


19,455 328, 329 248 240

48,157,192,221,496

Pyrophosphoric acid Pyrosulphates Pyrosulphuric acid

....

Rey, Jean Rhigolene Roasting Rochellesalt

12

485
231 261 8 343

Rocks
Rose's metal

Qualitative Analysis Quantitative meaning


.

bols,

formulas,

tions

236,368 of symand equa88


. .

Rosin Rust ...


Safety lamp matches
Salt
acid "

484
12

Quartz Quicklime Quinine

Quinone
Radicals

8,359 144,394 498 424


.

24 322

Epsom

"

Glauber's

147,375,382 147 403 384


147

Radium
Reactions
classes of

90, 145, 190 403

normal
Saltpeter
(niter)

endothermic
equilibrium exothermic
reversible
. .

3,9 78 291

Salts, basic

degree of ionization of
electrolysis of

....

388 148 160


166 152 147 113

157,192,219,221 291 223


100 330 321 410 46
301

nomenclature of normal and acid


properties of

stages of

Realgar

Red phosphorus Red precipitate


Reducing agent
hydriodic acid

Saponify Saturated compounds Saturated solution

316 207 286 Reducing flame 46 Reduction 367 by carbon 46 by hydrogen of potassium nitrate by lead, 212 Refrigerating agent, ammonia 187 as a Relation of volume of a gas to 32 pressure 78, 161, 162 Replacement

hydrogen peroxide nascent hydrogen

379,496 482 68 352 Scandium, properties predicted Scheele 15, 98 Scheele' s green 335 Schweinfurt's green 335 Sea-water 56

....
.

Semipermeable cell
Series, electromotive

130

....
.

Shells
Siderite, or spathic iron ore Silica
Silica skeleton

Silicates
Silicic acid

anhydride Silicon

161,370 267 436 . 356 372 360 360 359 356


.

XXX
Silicon carbide

INDEX.
359 357 359 357 357 358 358 419 423 423 422 423 420 423 423 422

Sodium
"

tetraborate

384
384,

compounds
dioxide

thiosulphate zincate

hydride occurrence and preparation


tetrachloride
tetrafluoride

" Softening water

....

Soils

Solder
Solids, diffusion of solution in liquids

Silver

408 59, 397 8 473 85 68

bromide
chloride " " coin

Solubility curves
factors of

and compounds
extraction of
iodide
nitrate

"
sterling

"...
.

Solute Solution
boiling point of

character of a
effect of

67,70,71 68 68 67 67 ... 70, 155 67


157

-plating

properties

and uses

Slag Slaking

of lime

Smalt
Smelting of silver

Smoke
Soap Soda-ash
Soda, crystallized

421,422 443 144,395 452 420 288


381

composition of a temperature on energy changes during equilibrium in freezing-point of a


. .

...

....
.

68 73 157, 219 70,155


71

of gases

of liquids of solids
of starch

70
67 502

379,386,497
382 183 375 47, 62

saturated

67,72,220
*
.

Soda-lime

Sodium
action
. . . .

supersaturated temperature changes during

upon water 112,377 amalgam and water, quantitative study


of the reaction

Solutions,

electric

conductance
.

of,

properties of Solvay, or ammonia, process

72 73 156 70

380
67 4 136 61

arsenite

63 335

Solvent
Specific gravity

bicarbonate carbonate
chloride

compounds
cyanide dichromate
ethylate

261,382 267,380 382 317 ffg. 384 464 377, 486

Specific heat
of

water

table

Spectroscope
Spelter Spiegeleisen
.

Appendix iii Appendix xii 407 440

62,378,379 nitrate 209,383 oxides 377 382 phosphate 376 preparation and properties 383 sulphate
hydroxide
.

Spontaneous combustion Stability of compounds


.

...
.

25

Stages

of reactions

Stalactites

23,291 100 267


pres-

Standard temperature and


sure

36

sulphide
sulphite

384

239

Stannates 4^4,475 475 Stannic acid Stannic and stannous compounds,474

INDEX.
Stannites 474,475 Starch 502 Stassf urt deposits 385 States of matter, physical 5, 85 Steam and its dissociation .... 63
.

XXXI
of

Sulphur, uses
water

Sulphuric acid

and sulphates, test chamber process .... 241,242


contact process
diluting

230 232 142,241 for .... 249


241,242 108

volumetric composition of

Stearin
Steel
alloys

441

ffg.,

tempering of Sterling silver Stibine Stibnite

Stoneware, porcelain, china Storage battery Strontium compounds


or Structural, formulas

53 497 447 445 445 422 340 337 434 471 400
199

English process

fuming
hydrates of

241,242 240 245

manufacture
properties of

of

purification of reduction of

.......

uses of

Sulphuric anhydride

constitutional,

Sulphurous acid Sulphurous anhydride

....

Structure,

effect

on properties

.317
498 397
191

Strychnine Stucco Sublimation Substances amorphous


crystalline
stability of
. .

Supersaturated solutions Suspension

Symbols

241,242 245, 246 244 246 247 240 239 239 ... 72 67 87

1,22 74 73

and equations, quantitative meaning of and formulas and formulas, how to represent multiples of

88 87 89 452

Sugar, cane
fruit

......

183,208,248,291 260,499,500 501

Sympathetic ink
Synthesis
of

water

grape malt milk

Suint Sulphantimonites Sulpharsenites Sulphates


Sulphides, formation groups of
of
.
.

200,500 499 499 384


341 337 247

System,

periodic

51,54 346 ffg.

Tannicacid Tannins

502
501 284

Tantalum

filament

Tartar emetic Tartaricacid


Tables.

340
142,495
.
.

232,233 236 234 precipitation of 239, 504 Sulphites 475 Sulphostannates 229 Sulphur, chemical properties of 231 compounds of 237 dioxide 237, 238 dioxide, properties of 227 occurrence and preparation 228 physical properties of 240 trioxide
.
.
.

Appendix v Appendix iii 65, 80 equivalent weights correction of barometer for


aqueous tension atomic weights
.

Appendix temperature heat of formation and solution,


. .

xii

metric equivalents
periodic

Appendix vi Appendix ii
354

....

reduction to standard temperature and pressure, Appendix ix

XXX11
Tables.
solubility, qualitative,

INDEX.
Turnbull's blue
450
484 341 435 482 479 479

Appendix
solubility,

vii

Turpentine Type-metal
Ultramarine Unsaturated compounds Urea
Uric acid

quantitative,

Appendix
solution

viii

tension

of

metals

(electromotive series), Appendix x specific gravity Appendix v Appendix iii specific heat .... vapor tension of water Appendix v
.
. .

Valence
of

115,158,163,190,199
.

multiple

weight of
gases

liter

of

several

members of argon family


. . .

118 119

Appendix v
29
pressure,
re-

of radicals

118,190

Temperature Temperature and

Vapor density methods


Vaseline

.125
485 425 494

duction to standard,
36,
critical

Vein-mining of gold
ix

Appendix

177

Verdigris Victor Meyer's


density

method

for

vapor
125

68 23 kindling of ignition 23 relation of volume of a gas to, 30 Tempering and annealing steel, 445
effect of,

upon solution

...

Vinegar
Volatile

494
191
of

Volume
of

a gas,

relation of pres-

sure to

32
of

Ternary compounds
Test reactions

....
....

95, 151

a gas, relation
ture to
of

tempera-

Tetrachlormethane Theine
Theory, atomic
ionization

molecular

Thermite Thiophene
Thiosulphates

160 236,492 499 80 157 83, 84 287, 288, 431 483 249
13,

30
definite

Volumes, laws
multiple

and
121

Volumetric analysis, use manganate in

of per-

composition of steam composition of hydrogen chloride

....
.

458 53
Ill

285,292 472 ffg block 472 occurrence and preparation of, 472 473 plate 473 properties and uses Tincture 70

Thorium dioxide

composition of ammonia meaning of an equation

192, 193
. .

195

Tin and its compounds

Water, action

of metals

upon
of

62
104

analysis of

50, 57

and chlorine, action and potassium


boiling of

....

Toluene Toning, photographic


Transpiration Trituration Trough, pneumatic

276,483 424 42 230


17

composition of
dissociation of
distilled

drinking
electrolysis o

Tube,

safety, or thistle
. .

Tungsten filament

39 284

formation of
gas process

63 58 20 62 58 56 50, 165 43 276

INDEX.
Water,
glass

XXX111
470 255
343 485 440

361

White-lead

59,397 76 mechanically enclosed .... 56 natural, and its impurities nature of 50 occurrence of 55 of crystallization 75,92,93 of hydration 75 60 properties of 57, 38, 432 purification of sea 56 397 softening of 232 sulphur 54 synthesis, by weight
. .

hard and soft

Wood charcoal
Wood's metal

Wood spirit
Wrought
iron
.

Xenon
Xylene
Zero, absolute

172, 353
.

483

31

Zinc
chloride

compounds
dust
oxide

synthesis, by volume vapor in the atmosphere


.

51

175
4

Weight
by multiple proportions by Weights, equivalent Welsbach burner
definite proportions
.
.

sulphate and sulphide

....
. .

(it

55 70 138 285

used in desilvering load


uses of

Zincates

407 409 408 407 409 409 421 408 408


187

Zymase

LABOEATOKY EXERCISES
THE "ESSENTIALS OF CHEMISTRY"

JOHN

C.

HESSLER,
AND

PH.D.

PROFESSOR OF CHEMISTRY, THE JAMES MILLIKIN UNIVERSITY; LATE INSTRUCTOR IN CHEMISTRY, THE UNIVERSITY OF CHICAGO, AND THE HYDE PARK (CHICAGO) HIGH SCHOOL

ALBERT

L.

SMITH, PH.D.

INSTRUCTOR IN CHEMISTRY, THE ENGLEWOOD HIGH SCHOOL, CHICAGO

EEVISED
BY

(1912)

JOHN

C.

HESSLER

ov rroAA' dAXa

BENJ. H.
BOSTON

SANBORN &
NEW YORK
1912

CO.
CHICAGO

Copyright, 1912,

BY JOHN

C.

HESSLER.

dlir

Sort

^tll

SAMUEL USHER 176 TO 184 HIGH STREET


BOSTON, MASS.

CONTENTS.
LABORATORY EXERCISES.
EXPERIMENT.
I.

PAGE.

The Bunsen Burner


Manipulation of Glass Tubing Solution, Filtration, and Evaporation Effect of Heat upon Oxides

....
....
...

II.

III.

IV. V.
VI.
VII.
VIII.

4 7
8
11

Oxygen
Per Cent of Oxygen in Potassium Chlorate Kindling Temperature

13 13

Hydrogen
Burning of Hydrogen and Reduction Equivalent Weight of Magnesium
Physical Properties of Water
of Oxides
.

IX.

16

X.
XI. XII. XIII.

17
19

Chemical Properties of Water Equivalent Weights of Magnesium and Oxygen,


Solution and Crystallization
Precipitation
Solubility of Potassium Chloride of Crystallization

21

XIV.

XV.
XVI. XVII.
XVIII.

Water

Efflorescence and Deliquescence

XIX.

Per Cent of Water of Crystallization


Definite Proportions

XX.
XXI. XXII.
XXIII.

Chlorine

Hydrogen Chloride Weight of a Liter of Oxygen


Properties of Acids
Properties of Bases
Properties of Salts Neutralization
.

XXIV.

XXV.
XXVI. XXVII.
XXVIII.

23 25 25 26 27 28 29 30 32 34 36 38 40
41

42

XXIX.

Normal and Acid Salts Normal and Acid Salts Continued


iii

43

45

CONTENTS.
EXPERIMENT.
PAGE,

XXX.
XXXI.
XXXII. XXXIII.

lonization

Hydrolysis and Replacement

Nitrogen

Ammonia
Nitric Acid
Nitrites

XXXIV.

XXXV.
XXXVI. XXXVII.
XXXVIII.

Nitrogen Tetroxide Nitric Oxide Nitrous Oxide


Physical Properties of Sulphur

XXXIX.
XL.
XLI. XLII.
XLIII.

46 48 49 50 53 55 56 57 59 60
61

Chemical Properties

of

Sulphur

Hydrogen Sulphide
Sulphur Dioxide Sulphuric Acid
Sulphates

XLIV.
XLVI.

62 64 66 67
69 70
71

XLV. Carbon

XLVIL
XLVIII.

Carbon Dioxide, Carbon Dioxide,


Reduction.

II

Effect of

Heat on Carbonates

...

71

XLIX.
L.

LI.

Flames Bromine Iodine and Hydriodic Acid

72 73

75
76

LII.
LIII.

LIV. LV. LVI. LVII. LVIII. LIX.

Comparison of the Halogen Acids Hydrogen Peroxide Phosphorus and Phosphoric Acid
Arsenic

77 78

80
81

LX. LXI.
LXII. LXIII.

Antimony Bismuth Borax and Boric Acid Sodium Compounds Potassium Compounds Ammonium Amalgam.
Alkali Metals Calcium Strontium and Barium

82

83 84
85
Distinctions between the
87
.

LXIV. LXV.

Magnesium
Zinc

8 89 90
91

LXVL

Equivalent of Zinc
iv

93

CONTENTS.
EXPERIMENT.
PAGE.

LXVII. LXVIII.

Cadmium
Mercury Copper
Silver

LXIX.

LXX.
LXXI. LXXII.
LXXIII.

94 94 96 97 98 100 102
103
104 106 107 109 110
Ill

Aluminum
Iron
Nickel and Cobalt

LXXIV.

Manganese Compounds

LXXV.

Chromium Compounds

LXXVI. Lead LXXVII. Tin


LXXVIII.

LXXIX.

LXXX.
LXXXI. LXXXII.

LXXXIIL LXXXIV. LXXXV. LXXXVI.


LXXXVII.

Composition of Carbon Compounds Hydrocarbons Ethyl Alcohol Ethyl Ether Aldehydes Acetic Acid and Acetates Other Organic Acids

113 113

114
115

Soap Carbohydrates

116

Some Principles of Qualitative

Analysis

....

118 119

PREFATORY NOTE.
" These laboratory exercises form a part of the Essentials of Chemistry," and contain specific directions for laboratory work. All the exercises are intended for the student, and are so arranged that they may be used in schools having either one-hour or two-hour laboratory
periods.

The experiments

require only

common

materials and

The quantities of materials have simple apparatus. been stated definitely and accurately. Where possible,
the directions call for fractional parts of a test tube, so that unnecessary weighing may be avoided. The test

tube meant
laboratories.

is

the ordinary 5

Xf

inch tube found in most

In the revised edition of the laboratory exercises the order of the experiments has been altered to bring it into harmony with the revised text. Many of the
experiments have been rewritten, and several new ones have been added. The quantitative exercises are not numerous. They have been selected for their importance in showing the weight relations of chemical reacAll have been thoroughly tested, and have succeeded in the hands of average students. For the
tions.

quantitative experiments the object of the experiment and the method used have been described
earlier

briefly

at

the

beginning of the exercise, so that the

student

he

is

may have a better appreciation of the directions to follow and of the result sought.
vii

PREFATORY NOTE.
The
reviser will be glad to learn of any errors that may and to receive suggestions from

exist in the exercises,

persons interested.

AUGUST, 1912.

J.

C. H.

Vlll

LABORATORY DIRECTIONS.
(For the Student.)
1. Provide yourself with an apron and a pair of sleeves (rubber the best material for these) also with soap and towel, and a white cloth about a yard square. The cloth is to be used for is
;

wiping apparatus.
2.

Work by
and
Record

yourself;

and give

your,

own

descriptions, ob-

servations,
3.

calculations, not those of another.

the observations you make in connection See that your notes contain the answer to every question, direct or implied, that occurs in the laboratory exercise. Write neatly and distinctly. If the notes of
at once all

with an experiment.

two experiments occur on the same page, separate them by at least two centimeters of space.
4.

Have a

place for everything.

Throw away nothing

until

you are sure you are through with it. Throw nothing but Put other waste materials into the proper liquids into the sink.
receptacle.
5.

If

successful;

an experiment is unsatisfactory, repeat it until you are but first learn the probable cause of your error.

6. When you enter the laboratory, examine your table, and see that everything has been left as it should be by the persons

who

share the table with you. If anything the fact at once to the instructor.

is

wrong, report

When you
off,

leave, see that the water


is

and that everything on your table

in

and the gas are turned good order.

IX

LABORATORY

EXERCISES.

EXPERIMENT

I.

THE BUNSEN BURNER.


Apparatus. note below).
Materials.
a.

Bunsen

burner., test tube, test-tube holder (see

Matches, water.
carefully the

Take
b.

Bunsen burner on your desk. and a draw sketch of each part. apart, Put the burner together, close the holes at the base,
it

Examine

and connect with gas supply. To light the burner, turn on the gas and then hold a lighted match near the side of the burner and about onehalf a centimeter below its mouth. Note the character
flame; is it luminous or not? Now open the holes carefully until the luminous region has just dis" Bunsen " flame. For most appeared. This is the
of the

should be 7 to 10 centimeters (3 to 4 inches) holes of the burner should be open far enough high. to prevent a deposit of soot upon the object heated, but
it

work

The

not far enough to cause the flame to make a noise. c. Introduce quickly into the center of the Bunsen flame, one-half a centimeter above the burner, the head end of a match. Result? Is the gas in this region burning?

To

heat

an

object effectively,

place

it

higher

up in

the

flame; the best place is just above the apex of the dark, inner cone of unburned gas. Locate this region.
i

LABORATORY EXERCISES.

d. Put 5 c.c. water into a test tube, and make a note of the height of the column of water in centimeters. Whenever you are asked to take 2, 5, 10, etc., cubic centimeters

of anything, refer to this experiment, and use the length of the column just measured as your unit. To do e. Heat the water in the test tube to boiling.
this properly

have the outside

of the

tube dry;

hold

the tube in the holder, and incline the tube at an angle Then introduce the of about 45 to the table top.

bottom

the flame.

tube into the effective region (cf. c) of Heat only the part of the tube containing the liquid; if the flame strikes the glass above the liquid level, the tube may crack. Do not hold the tube still, but move it gently in the flame. When boiling begins, raise the tube a little above the flame, so that always keeping it inclined, the water may not " boil over."
of the
/.

These directions are general, and will apply whenever

you heat liquids in test tubes.


Note.

A very

convenient test-tube holder can be

made by

folding a piece of writing paper twice, so as to produce a strip about 1 cm. wide and 10 to 15 cm. long. This is placed about

the tube like a holder.


to the tube.

The

free ends are held together close

MANIPULATING GLASS TUBING.

EXPERIMENT

II.

MANIPULATING GLASS TUBING.


Apparatus.
gas burner,
file,

Bunsen burner, " wing-top


blast-lamp. Piece of soft glass tubing

"

or

illuminating

Materials.

more than 15 cm.

long,

one of ignition tubing 18-20 cm. long.

a piece of glass tubing 15 cm. long. To do the tubing a file mark in a plane perpenthis, dicular to the length of the tubing; grasp the tube in both hands, and place the thumb nails together opposite
a.

Cut

off

make on

the scratch. By pushing gently with the thumbs and at the same time pulling with the hands you will succeed in breaking the tubing so that the ends are fairly regular.
6. Round off (" fire-polish ") both ends of the 15 cm. tube by turning them about in the Bunsen flame until the edges become red hot. Let the ends cool. c. Bend the 15 cm. tube at its middle into the form of a

right angle.

For
a

produced by

this purpose use a flat " "

Bunsen flame
or

wing-top

attachment

flat

illuminating flame.

Take the tube


hold
its

in

both hands, one at each end, and

flame.

central part lengthwise with and over the flat At the same time twirl the tube between thumbs

and
it

forefingers.

Then lower

the tube

keep turning

you
d.

into the upper part of the flame, and heat until Then bend gently find that the glass is fairly soft.

to a right angle.
If

the bend

you used the Bunsen by closing the holes

flame, anneal the glass at


of the burner

and allowing

LABORATORY EXERCISES.

the hot glass to cool first in the smoky flame. the bend is covered with soot, support it so that

When
it

will

not touch a cold object. off the soot.


e.

When
"

the tube

is

cold,

wipe

of hard glass by melting a piece of hard glass tubing 18-20 cm. long at its middle Do this by grasping one in the flame of a blast-lamp. end of the tubing between the thumb and forefinger of

Make

two

"

ignition tubes

each hand, and twirling


glass softens

it

rapidly in the flame until the

and the walls of the tubing come close Then draw the two halves apart, but do not together. break the connection until the glass becomes stiff. Now break the connecting tube, and melt off the drawn-out For this use a glass where the tube becomes narrow. small blast-lamp flame. When the closed end of the " " the open end in the ignition tube is cool, fire-polish
blast-lamp flame.

EXPERIMENT

III.

SOLUTION, FILTRATION, AND EVAPORATION.


Glass rod 15 cm. long (unfinished), file, two Apparatus. beakers of about 50 c.c. capacity, ring stand, wire gauze, funnel, funnel support (small ring of ring stand), evaporating dish, test tubes, mortar.
Materials.

Marble,

salt,

dilute

hydrochloric

acid,

filter

paper.

Make a glass stirring rod 15 cm. long, cutting off a piece from a larger one, just as in Experiment II, a. Round off both ends in the flame.
a.

SOLUTION, FILTRATION,

AND EVAPORATION.

Taste a bit of marble, then put it into a test tube and add a drop of dilute hydrochloric acid. Results? Do the same with a pinch of salt, and state results. How can you distinguish marble from salt? b. In a mortar powder a lump of marble, add to it about | of a test tube of salt, and grind the two thoroughly together. Put the mixture into a beaker with about 20 c.c. cold water, and heat the beaker over the
flame until
see that

contents boil. Before heating the beaker dry on the outside, then place it upon a wire gauze supported on the ring stand. Move the flame about under the gauze until the beaker has become
its
it is

then put the burner under the center of the The height of the gauze above the burner should be so great that the bottom of the beaker may be a little above the apex of the dark inner region of the flame.

warm;

beaker.

Note.

Always follow

these directions

when you

are heating
is

a beaker, an evaporating dish, or a flask, unless there What bespecial reason for not doing so.

some

comes

of the salt?

Of the marble?

You need c. Next, filter the solution. a funnel, a support (see above), a filter, the glass rod made in a, and a second
beaker.

Fold the circular

filter

twice in lines
Press the

at right angles to each other. folded edges between thumb


finger,

and

foreFlGt 93

but not between the


so that
.

the

filter

it

shall
fits

Open form an innails.

verted cone which just


conical surface
is

the funnel.

One-half of the

made up

of three of the quarters into

LABORATORY EXERCISES.

which the paper was folded; the remaining quarter of the paper makes up the other half of the cone. d. Hold the filter in place in the funnel, and wet it completely; it should adhere everywhere to the inner
into the

surface of the funnel, and its point should extend a stem of the funnel.

little

down the glass rod to the filter. rod should touch the lip of the beaker; glass and the stem of the funnel should touch the side of the beaker beneath it.
Pour the
salt solution

The

solid

Always follow these directions in filtering an insoluble from a solution. e. Does anything remain on the filter? We call it
Test

What passes through is the filtrate. the residue as you did the marble and salt in a.
the residue.
is it?

What

A substance which remains mixed with a liquid, but not dissolved in it, is said to be " suspended in/' or " held in suspension by " the liquid. A suspended substance becomes, after filtration, a
residue.
f. Pour the filtrate of c into an evaporating dish, and heat (for precautions, cf. 6) over the flame. Boil off the water until a solid begins to separate out; then set the dish aside until it is cold, or until the next laboratory

What is the solid obtained? period. Is this separation of the salt from the or a chemical operation?

marble a physical

EFFECT OF HEAT UPON OXIDES.

EXPERIMENT

IV.

EFFECT OF HEAT UPON OXIDES.


Apparatus.

Small ignition tube of hard

glass,

rubber con-

necting tube, delivery tube, pneumatic trough, test tube, ring stand, clamp. Materials. Pine splinter, mercuric oxida, lead dioxide.
a. In a small tube of hard glass sealed at one end and " " about 10 cm. long ignition tube place a layer of mercuric oxide not more than onehalf a centimeter

thick.

In

a basin

con-

taining water, invert a test tube of water.

See that no air bubbles


test

remain in the
tube.
" Vessels
FIG.
94.

for holding

water over which gases are collected are

pneumatic troughs." Attach to the ignition tube by means of a piece of rubber tubing a delivery tube long enough to reach to

called

bottom o/ the pneumatic trough. Support the and delivery tubes so that the closed end of the ignition tube is only a little lower than its other end, and
the
ignition

so that the mercuric oxide

may

be heated in the hot

portion of the
b.

Bunsen

flame.

Begin

to

Note any change

heat slowly, keeping the flame in motion. Afterward heat in color of the oxide.

LABORATORY EXERCISES.

strongly with a steady flame until all of the powder Collect over water anything that escapes disappears.

from the delivery tube by allowing

it

to displace the

When the operation is over, water of the test tube. remove the delivery tube from the water before removing the
flame.
c.

Why?

Cover the mouth of the test tube under water with the thumb, remove tube from water, invert, and introduce a pine splinter with a spark on the end of it. Result?
Is the gas in the test
d.
its

tube air?
is

What
table.

is it? it

When

the ignition tube


is

cool, invert

and

strike

open end sharply against the


this?

Result?

What
it

substance
collect?
e.

On what
it

Why

did

part of the tube did not pass out of the tube?

Would you
Repeat

call this

is

mercuric oxide made?


/.

a chemical change, or not? Consult a text.

How

a, 6, c,

mercuric oxide.
it

and d, using lead dioxide instead of Does the powder disappear? Does

give off a gas?

What is the gas?

What

is

the residue?

Answer

e for this case als,o.

EXPERIMENT
OXYGEN.

V.

Mortar and pestle (?), test tubes, ring stand Apparatus. and clamp, one-holed stopper, delivery tube, pneumatic trough, 4 collecting bottles, glass or cardboard cover, deflagration
spoon.
Materials.

Powdered potassium chlorate and manganese


at

dioxide, pine splinter, sulphur, iron wire (picture cord) least 15 cm. long, lime-water, magnesium wire or ribbon.

OXYGEN.
a.
c.c.

On

a clean piece of writing paper mix carefully 6-8

powdered potassium chlorate with about 3 c.c. powdered manganese dioxide. If the substances are not found in powdered form in the laboratory, grind

them
b.

separately, in clean mortars, before mixing.

Before you use the whole mixture, test the quality of a sample (1 c.c.) by heating it gently in an open test If there is any evidence of violent combustion, tube. or if large sparks appear, reject the mixture, and make a
fresh one.
dust, etc.
c. If the mixture is satisfactory, put it into a test tube supported by a clamp attached to a ring stand. The test tube is then fitted with a one-holed stopper and a delivery tube reaching under water in a pneumatic

few small sparks indicate only traces of

trough.

Have
trough.

4 bottles

filled

with water and inverted in the

To invert bottles in the trough without letting in air, fill them to overflowing with water, cover their ntouths
with
slips of glass or

the bottle, and remove the covers. To remove a bottle

cardboard, press the latter against Then invert quickly under water.
full of gas

from water,

slip

under the

mouth of the bottle, under water, a glass or cardboard Leave a filled cover, and hold it in place as before.
bottle with its

mouth under water

until used,

if

possible.

be placed upright or Whether inverted upon the table depends upon the specific gravity of the gas. d. Heat the test tube gently from the top of the mixture downward. Regulate the flame so as to keep the
a bottle of gas shall

10

LABORATORY EXERCISES.

evolution of gas steady, but not violent. Keep the flame in motion, so as not to soften the glass. When the collecting bottles are full, first take the
delivery tube out of the water, flame. this precaution?

and then remove the

Why

is oxygen. Into one bottle of the gas put a glowing splinter as in Experiment IV, c. Result? Gradually lower the
e.

The gas

splinter into the bottle until combustion stops. becomes of the splinter? Of the oxygen?

What
calcium

To

the contents of the bottle add 5

c.c.

hydroxide solution (lime-water), cover with the hand, and shake vigorously. Result?

N.B. Lime-water reacts with carbon dioxide to a This give white, insoluble solid, calcium carbonate. serves as a test for carbon dioxide. Where does the carbon of the carbon dioxide come from? /. Note the odor of the gas in the second bottle. Then put into the bottle a deflagrating spoon containing
burning sulphur. Light the sulphur by holding the spoon in a flame. Have a cardboard cover with a small hole for the handle of the deflagrating spoon, and keep the bottle covered until combustion stops. Results? What becomes of the sulphur? Of the oxygen? Note the odor of the gas now in the bottle. Does this

Name
it

gas support the combustion of a splinter? Try it. the gas. Add 5 c.c. of water to the bottle, shake

about, and then put in one piece each of red and blue litmus paper. Result?
g.

Have

upright on the

the third bottle of oxygen covered and set table. Draw aside the cover for a moment

OXYGEN.
while*

11

/ou pour in sand enough to cover the bottom of the bottle; then replace the cover. Melt some sulphur in a deflagrating spoon, and dip into it one end of a piece of iron picture cord. Light the
sulphur
oxygen.
action
tip,

and

at once

hold the iron wire in the bottle of

Why
h.

Keep the wire in the gas until Describe the product and name it. was the iron tipped with sulphur? Hold a piece of magnesium wire or ribbon by means
Result?
ceases.

of iron tongs, or make a hook upon it, and hang it on the reverse end of a file. Light it in the Bunsen flame,

and hold it in the fourth bottle Name and describe the product.

of oxygen.

Result?

a few drops and then in the to the of water bottle, product more) (not bring into contact with it one piece each of red and blue
litmus paper.

Add

one

is

changed?

Let them remain some time. Compare with the result in/.

Which

EXPERIMENT

VI.

PER CENT OF OXYGEN IN POTASSIUM CHLORATE.


Apparatus.

Hard

glass test tube,

Bunsen burner, clamp,

and ring stand.


Materials.

been dried in an
a.

Pure, powdered potassium chlorate which has air bath at 120 C.

The

It

is

object of this experiment is given in the title. attained by decomposing completely a weighed
of pure,

amount
the

dry potassium chlorate and weighing


that
remains.

potassium

chloride

The

material

lost is oxygen.
b.

Weigh a

clean,

dry hard-glass test tube accurately,

12
and put into

LABORATORY EXERCISES.

it about 5 c.c. (a layer 1 inch thick) of the potassium chlorate. Wipe off any particles that may adhere to the mouth of the test tube. Weigh the test tube and chlorate accurately, and record the weights

as directed in
c.

d.

Support the test tube of b by means of a clamp and a ring stand, keeping the open end of the test tube a little higher than the closed one. Have the clamp near the open end. Begin to apply heat cautiously, with a
small,
all

moving

flame.

Then heat more

strongly, until

the chlorate melts, and the melted substance is in effervescence. Do not let the effervescence become so
rapid that much white smoke is driven out of the test tube. When all effervescence seems to have stopped, heat more strongly still, so that every part of the contents
is completely melted and ceases to effervesce. Then let the tube cool, weigh it, and record the result. To make certain that the decomposition is complete, heat the tube again, cautiously at first, then strongly, and

no

weigh the tube once more. Continue this until there is difference between successive weighings. We call
"

this

heating to constant weight."

Use the

last

weight

in calculating results. d. Record the results as follows

Grams.

Wt.

of test tube

+ potassium chlorate
alone

potassium chlorate taken

Wt.
*

of test tube

+ potassium chlorate chloride +

= = =

The wt. of oxygen evolved Per cent of oxygen =


.
.

HYDROGEN.

13

EXPERIMENT

VII.

KINDLING TEMPERATURE.
Apparatus.

Wire gauze at

least

15 cm. square, Bunsen

burner, tongs. Matches. Material.

Hold the wire gauze, by means of your tongs, 7 cm. Bunsen burner. Have the holes of the burner the Bunsen flame. Now turn on the gas and for as open a burning match from above down to the center of bring
a.

above the

the gauze. Result? Why does not the gas below the gauze take there gas below the gauze? Prove it.

fire?

Is

6. Let the gauze cool; and then bring it down upon the Bunsen flame until the gauze is 6 to 7 cm. above the top of the burner. Result? Hold the gauze in

place until

it

becomes red

hot.

Result?

Explain.

EXPERIMENT
HYDROGEN.

VIII.

Generating flask, or bottle of 250 c.c. capacity, Apparatus. two-holed stopper, funnel tube, right-angled tube, rubber conof glass or of nector, delivery tube, pneumatic trough, squares bottles (250 c.c.). wide-mouth more or two collecting cardboard,

Materials.
of acid to four
solution.

Zinc, dilute sulphuric acid (one part

by volume

volumes of water), pine

splinter, cupric sulphate

14
a.

LABORATORY EXERCISES.
To
a 250
fit

c.c.

the bottom
is

bottle containing enough zinc to cover a two-holed stopper. One of the holes

of the

for a funnel tube reaching to within one-half a centimeter bottom of the bottle when the stopper is in place
;

the other hole contains a bent tube attached by a rubber connector to a delivery tube. The delivery tube reaches
to a pneumatic trough containing water and inverted.
6.

two

bottles filled with

Caution.

(about three feet)

Keep all flames at least one meter away from apparatus in which hydro-

gen
c.

is

made.

tight,

See that the stopper of the generating bottle is and add enough of the dilute sulphuric acid to
of the funnel tube.
in
bottle,

immerse the lower end


Tell

what takes place

funnel tube, and

Explain each phenomenon. If action is not vigorous add a few drops of copper sulphate solution. Result? If evolution of gas ceases or becomes slow before you are through, add more acid. The gas produced is hydrogen. d. Fill the two "bottles with the gas and refill them

pneumatic trough.

after

using.

Reject

the

first

bottleful

collected
it?

by

turning it mouth upward. turn it mouth upward?

Why

not use

Why

its

bottle inverted and introduce into middle part a burning pine splinter 15 to 20 cm. long. Hold the splinter steady 20 to 30 seconds. Result? Does the gas burn? Where? Does the splinter con-

Keep the second

tinue to burn in the hydrogen? Is hydrogen combustible or a supporter of combustion?

Turn a third bottle of the gas mouth upward one minute, and repeat the test with the burning splinter.

HYDROGEN.
Results?
of

15

From

the result compare the specific gravity


air.

hydrogen with that of


e.

Place the
of

mouth

an

together and apply a lighted match to the lower bottle.

of a fourth bottle of gas over the upright bottle of air. Hold the bottles reverse their positions. After one minute

mouth

Result?

To
/.

the upper.

Result?

What

conclusion as to the

diffusibility of

Have
it,

incline

hydrogen? (and last) bottle only half full of gas; and then raise it slowly from the water so
fifth

that air displaces the remaining water. Carry bottle, mouth down, to a flame. Result? Explain difference
free

between this from air.


g.

result

and the combustion


tell

of

hydrogen
is

From

the experiment

whether hydrogen

very

soluble in water, or not.


h.

bottle into

or

if

liquid and the unused zinc from the a beaker. If the zinc has all dissolved, there seems to be enough acid to dissolve all of it,

Pour the

add more zinc. Leave until action ceases. has anything separated from i. Examine the beaker;
solution?
If
so, re-dissolve
filter
it

by heating the beaker

on the wire gauze, and

(Care!) Collect the filtrate in another beaker or an evaporating Result? dish, and let it stand some hours.

hot.

The substance you obtain

is

crystallized zinc sulphate.

16

LABORATORY EXERCISES.

EXPERIMENT
OXIDES.

IX.

BURNING OF HYDROGEN AND REDUCTION OF


Apparatus. Hydrogen generating bottle of Experiment VIII, two-hole stopper, funnel tube, right-angle tube, rubber connector, a second right-angle tube of slightly larger diameter than the
other, beaker,

and

test tube.

Materials.

Zinc,

dilute

sulphuric

acid,

cupric

sulphate

solution, cupric oxide (in wire


a.

form

if

possible).

Arrange the apparatus of Fig.

95.

Into the longer

(horizontal)

arm

of the

second right-angle tube (B) put cupric oxide in wire form. To the zinc in the
.

generating bottle (A) add a few drops of cupric sul-

phate solution, then dilute


sulphuric acid.

When

the

gas comes

off readily,

hold

over the end of the exit tube (C) a cold, clean


beaker.

Does any deposit


of

of moisture appear?
b.

Over the end


a
test

FIG.

95.

invert

tube,

and

minute carry it, mouth down, to a flame at least 4 feet away. Note what happens, and at once return the test tube, still mouth down, to the jet C, Continue until the hydrogen is lighted at C (consult 50, pg. 41, of
after a
text).

What

is

the color of the hydrogen flame at

first f

EQUIVALENT WEIGHT OF MAGNESIUM.


After the end of
cf.

17

411 of text.
Is

flame.

has become hot? For the reason, Hold a cold beaker over the hydrogen there a deposit now? What is it? How

formed? c. While the hydrogen flame is burning, heat the tube at B, under the cupric oxide, first with a moving flame, then more strongly. Do not heat it enough to melt
it

was

the glass.

What change
tube?

the solid substance left?

occurs in the cupric oxide? What is Is there any deposit in the

What

is

it?

when hydrogen burned?


cupric oxide?

What was the source When it was

of the

oxygen

passed over

Define reduction.

EXPERIMENT

X.

EQUIVALENT WEIGHT OF MAGNESIUM.


tle

Balances, pneumatic trough, wide-mouth bot(250 c.c.), graduated jar, glass or cardboard cover. Materials. Magnesium wire, dilute sulphuric acid.

Apparatus.

The object of this experiment is to find how many grams of magnesium replace 1.008 grams of hydrogen. The resulting number is called the equivalent weight of magnesium. The weight of the hydrogen is calculated from the volume. The volume actually obtained is " " to C. and 760 mm. From this we get the reduced
a.

weight, for 1 1. of hydrogen at 0.09 gram (cf. Appendix v):


b.

C. and 760

mm.

weighs

In a pneumatic trough containing water to the

18

LABORATORY EXERCISES.

depth of about 3 cm. place a piece of magnesium wire There should be the exact weight of which is known. not more than 0.2 gram. Get the exact capacity in cubic centimeters of a widemouth bottle by filling it with water and pouring the water into a graduated vessel. The bottle should hold
at least 250
c.

c.c.

Half

fill

the bottle with dilute sulphuric acid, then

add enough water to fill it, and invert it in the pneumatic trough as far from the magnesium as possible. See that the bottle is free from air bubbles. Now slide the

mouth
Result?
d.

of the bottle,

under water, over the magnesium.


let

When

all

the metal has disappeared,

the col-

Then lected gas cool to room temperature for 5 minutes. add water of room temperature to the bowl, if necessary,
so that the level of water in bottle

and bowl

shall

be the

same.
it

Why?
by grasp-

Protect the bottle from the heat of the hand


ing

with a towel; then slip under its mouth a glass or cardboard cover, and invert quickly, so as to lose none of the water in the bottle. Bring a flame to the mouth of the bottle at once.
Result?
tion

The gas is hydrogen. The other product of the reacis magnesium sulphate; it remains in solution.
Let your thermometer remain in the solution in the

bottle for five minutes; then read it, and call this the temperature of the hydrogen. Also read the barometer.

Get the volume of the water remaining in the by means of a graduated vessel. Then obtain the volume of the hydrogen by difference. From the reading
e.

bottle

PHYSICAL PROPERTIES OF WATER.

19

of the barometer, in millimeters, subtract the "tension of water vapor," to get the partial pressure of the dry

hydrogen, and then reduce the volume of the hydrogen


to standard conditions.

Calculate the weight of the hydrogen, and solve the following proportion for x, the equivalent weight of
/.

magnesium.
Wt.
g.

of

magnesium

Wt.

of

hydrogen

::

1.008.

Record your results as


of

follows:
g.
c.c.

Wt.

magnesium taken

Vol. of hydrogen obtained

Temperature Barometer reading Tension of water vapor at


*
. .

C.

C.

mm. mm.
mm.
mm.

Partial pressure of dry gas C. and 760 Vol. of dry hydrogen at

c.c.

Wt.

of

dry hydrogen

g-

= Equivalent weight of magnesium

EXPERIMENT XL
PHYSICAL PROPERTIES OF WATER.
Ring stand, wire gauze, 100 c.c. flask, one-hole Apparatus. cork stopper, doubly bent delivery tube, test tube, beaker,

Bunsen burner, thermometer, evaporating Materials. Hydrant or well water,


crushed or chipped
ice.

dish.
distilled

water,

salt,

20

LABORATORY EXERCISES.
of

a. Distillation

Water.

Set

up the apparatus

of

Fig. 96.
it

the flask with hydrant water, support on the wire gauze, and attach the doubly bent delivery
fill

Half

tube.

This reaches to a test tube standing in a beaker


(or bottle) of cold water.

The
both

test

tube serves condenser and


Distill

as
re-

ceiver.

the water
fills

until the distillate half

the test tube.


distilled water.

Taste the

Evaporate

c.c.

of

it

to dry ness in

a clean evaporating dish. Note if there is a residue,

and

its

amount.

For com-

FIG.
b.

96.

evaporate 5 c.c. of hydrant water to dryness, and give the result. Define distillation.
parison,

(use
fill

Boiling Point of Water. Support a flask securely clamp or extra ring) on the wire gauze of a ring stand, it one third with distilled water, and boil the water.
of the boiling
it.

the bulb of the thermometer in

water by immersing Do not read the temperature until it is constant. The bulb must be completely immersed. Now wipe the bulb of the thermometer dry, and hold the bulb in the escaping steam about 2-3 cm. above the level of the water. Compare the two temperatures, and write them down.

Get the temperature

Add more
temperature.

distilled water,

of a test tube of salt.

if necessary, and one-third Boil the salt water, and get its Also wipe the bulb of the thermometer

CHEMICAL PROPERTIES OF WATER.


perfectly clean

21

and dry, and get the temperature of the steam. Give the results. escaping Point of Ice ; a Freezing Mixture. c. Melting
beaker put about 30 c.c. of crushed or stir it with the bulb end of the therchipped ice, mometer. Have the bulb completely immersed. Give the exact reading as shown by your thermometer. Is
Into a 50
c.c.

and

your thermometer correctly graduated? Now add half a test tube of salt to the crushed ice, and stir the mixture with the thermometer. What is the temperature? Will any other substances give freezing mixtures with
ice?

Consult text.

EXPERIMENT

XII.

CHEMICAL PROPERTIES OF WATER.


Apparatus.

Tongs

or

forceps,

evaporating

dish,

small

wide-mouth
Materials.

collecting bottle, glass square.


solid

Sodium, water, blue and red litmus paper, sodium hydroxide, quicklime, anhydrous cupric sulphate.
a.

Action of Sodium upon Water. Do not handle sodium with wet hands, or with wet forceps. Do not put sodium into the waste On no account leave any sodium on or about jar.
Caution.

Sodium is usually kept 525 of text). What is the appearance of a freshly cut surface of sodium? Is sodium hard or soft? Heavy or light?
your desk or in your locker. under kerosene or ligroin (c/.
Fill

full

your smallest gas-collecting bottle three-fourths Draw of water, and cover it with a glass square.

22

LABORATORY EXERCISES.

aside the cover, drop in a small piece of sodium (not over 8-10 cubic millimeters in volume: size of a wheat grain),

and cover it at once. Note the action. When the sodium has disappeared, apply a lighted match to the Result? What gas is formed when sodium bottle.
reacts with

water?
fingers.

between the
effect,

Test the solution by rubbing it Result? If you get no decided

add a second piece of sodium (dry hands) exactly you did the first, and repeat the test. Put one piece each of red and blue litmus paper into the solution, and give the results. Compare with / and h. Experiment V, b. Add a small piece (same size as sodium used) of sodium hydroxide to 5 c.c. of water. Test the resulting solution with the fingers and with litmus, and comas

Conclusion? pare the effects with those of a. In an evaporatc. Action of Water with Quicklime. ing dish treat a lump of quicklime about the size of a
small hickory nut, or a large cherry, with water, as long as the water is completely absorbed. Do not have an
excess of water.
If

Note the

result after a

few minutes.

no

result appears, try the effect of

warming the dish

slightly.

If there is still no result, repeat the experiment with a second lump of quicklime. Use the quicklime prepared from marble, if possible. How is commercial quicklime made? Of what ele-

ments

is

it

slaking it? answers.


d.

composed? For what

What change
is

it

used?

takes place in Consult text for

Action of Water with Anhydrous Cupric Sulphate. Compare the colors of blue vitriol and anhydrous cupric
sulphate.

To about

1 c.c.

of

anhydrous cupric sulphate

EQUIVALENT WEIGHTS.

23

held in the palm of your hand add one or two drops of water. What two results do you notice? What is the
difference, as
vitriol

shown by this experiment, between blue and cupric sulphate?

EXPERIMENT

XIII.

EQUIVALENT WEIGHTS OF MAGNESIUM AND OXYGEN.


Apparatus.

Evaporating
tongs.

dish,

watch

glass,

evaporating

apparatus

(cf. b),

Materials.

Magnesium wire

or ribbon, dilute nitric acid.

a. The object of this experiment is to determine the number of grams of magnesium that combine with 8 grams of oxygen. The method used is to convert the

magnesium into magnesium nitrate (cf. 227 of text), and then to decompose the magnesium nitrate by heat 230 of text). The residue is magnesium oxide. (cf.
In a weighed porcelain evaporating dish weigh out accurately about 0.5 g. of magnesium wire or ribbon. Provide the evaporating dish with a watch glass cover

Draw this aside slightly, and to prevent spattering. add dilute nitric acid, a few drops at a time, until the metal has dissolved. Rinse the under side of the watch
glass

with 10

c.c.

of water, collecting the rinsings in the

evaporating evaporating in

dish.
6.

Remove

the watch glass cover

when

b. Evaporate the solution of magnesium nitrate (on a water bath or steam bath if possible; otherwise on a

wire gauze) until the residue

is

syrupy.

Be

careful to

24
avoid
loss.

LABORATORY EXERCISES.

Further evaporation over a flame generally causes spattering; but 1he heating may be continued Do this as safely if the flame is applied from above.
follows:

Hold the evaporating dish by means of iron or brass tongs grasped in the left hand, and carefully move the
is spread in a thin but not nearer to the of the the sides over dish, layer At the same than one centimeter. time hold the edge Bunsen burner in the right hand, move the flame gently

dish about, so that the syrupy liquid

round and round, and direct it upon the contents of the dish. By careful manipulation the magnesium oxide be obtained as an opaque powder. When the may decomposition of the nitrate seems complete, apply the flame from below again. Heat the dish to faint redness for five minutes, cool it, and get its weight. Record
your weights as in Experiment VI.

To make
heat
it

sure that the dish

is

at constant weight,
it

weigh

it.

carefully If there

once more to
is

redness, let

cool,

and

loss,

repeat the heating.

Record

the final weight. c. Get the weight of the oxygen that combined with the magnesium. Then solve the following proportion
for x:

Wt.

of

magnesium

wt. of oxygen
of

::

8.

Compare the equivalent


correct

.magnesium thus obtained

with that obtained in Experiment X.

What

is

the

amount?

oxygen
water?

quantities of hydrogen and of are- equivalent to this weight of magnesium?

What

In what proportion, by weight, are they combined in

PRECIPITATION.

25

EXPERIMENT

XIV.

SOLUTION AND CRYSTALLIZATION.


Apparatus.
Materials.
vitriol).

Beaker (50 c.c.), stirring rod. Potash alum, crystallized cupric sulphate (blue

a. Put 20 c.c. water into a beaker, add 10 grams powdered alum, and stir two minutes with the stirring rod. Does all the alum dissolve?
6.

Heat the beaker

carefully

on the wire gauze,

stirring

the contents.
c.

Result?

Conclusion.

and
d.
b.
it

stir

Set the beaker with the hot solution in cold water, rapidly until solution cools. Result?

Dry
cold.

Result?
is

the outside of the beaker, and heat again as in Let the solution stand undisturbed until

Result?

Compare with
c.c.

c,

and account

for

the difference.

Repeat a, b, c, and d, with 20 powdered blue vitriol. Results?


e.

water and 15 grams

EXPERIMENT XV.
PRECIPITATION.

Apparatus.
Materials.

Test tubes.

Solutions of lead nitrate, potassium chromate, barium chloride, and calcium sulphate. Dilute sulphuric acid;
alcohol.

26
a.

LABORATORY EXERCISES.
To
5
c.c. of

lead nitrate solution in a test tube add

an equal volume
sult?

of potassium chromate solution. ReLet tube stand ten to fifteen minutes. Result?
is

The
b.

precipitate
a,

lead chromate.

Repeat solution and


fifteen
c.

putting together hot barium chloride Result after ten to dilute sulphuric acid.

To

minutes? The precipitate is barium sulphate. 2 c.c. calcium sulphate solution add an equal
of alcohol.

volume
sulphate.

Result?

The

precipitate

is

calcium

Note.

The

insoluble solids

formed in a and b are not the

only products of these reactions; the other products are, however, soluble.

EXPERIMENT

XVI.

SOLUBILITY OF POTASSIUM CHLORIDE.


Steam bath, water bath, or wire gauze; evaji Apparatus. orating dish, balances. Materials. Powdered potassium chloride, distilled water.
a.

Make

a saturated solution of potassium chloride by

shaking 12 grams of the powdered substance in a clean flask with 25 c.c. distilled water at the temperature of the room. Continue shaking every little while for
tion,

Record the temperature of the soluand then weigh out accurately into your evaporatNow evaporate ing dish about 20 grams of the solution.
fifteen minutes.

(see b) the
is

water until the residual potassium chloride

perfectly dry,

and get

its

weight.

From

the results

WATER OF CRYSTALLIZATION.
calculate

27

how much potassium chloride will dissolve in 100 grams of water at the room temperature. b. If possible, evaporate the solution of a on a steam or water bath. If this is impossible, evaporate slowly
and
c.

carefully

on wire gauze, so as to avoid any


results thus
:

loss

by

spattering.

Record your

Grams.

Wt.
' .
.

of evaporating dish

+ water + KC1
alone

Wt.

Wt.
. '
. .
.

+ KC1 of evaporating dish + KC1


of

water

,,

,,

alone

Wt. Wt.

of

KC1
found
:

of water

Wt. KC1 found

::

100 grams :x.

EXPERIMENT

XVII.

WATER OF CRYSTALLIZATION.
Apparatus.
Materials.

Test tubes, iron saucer (sand bath). Crystals of zinc sulphate, of potash

alum

(po-

tassium aluminum sulphate), and of cupric sulphate.

Place a few crystals of zinc sulphate in a dry test Results? Is there evidence tube, and warm gently.
a.

of water?
6.
c.

Where?

Repeat a, using a crystal of potash alum. Results? Note the taste of another crystal of potash alum; then heat it strongly in an iron dish until no further
change occurs.
Results?

28

LABORATORY EXERCISES.

the ignited alum is cold, taste it. Result? water in a test tube, and boil carefully for When the water is cool, taste it. Result? five minutes. Assuming that heat simply drove off crystal-water

When
it

Place

in 5 c.c.

from the alum, upon what does the taste alum seem to depend? d. Heat a crystal of copper sulphate
strongly in
cold,

of crystalline

(blue vitriol)

an iron dish. Result? add a few drops of water to it.

When

the residue

is

Result?

Explain.

EXPERIMENT

XVIII.

EFFLORESCENCE AND DELIQUESCENCE.


Evaporating dish, beaker, watch glass. Hydrates of sodium carbonate (washing soda) and of sodium sulphate (Glauber's salt), solid potassium hydroxide, anhydrous calcium chloride.
Apparatus.
Materials.
a. Expose a bright crystal of washing for at least twenty-four hours. Result?
b.

soda to the

air

weigh into

Carefully weigh your evaporating dish, and then it accurately about 5 g. of bright crystals of

Glauber's salt (hydrate of sodium sulphate). Leave the dish uncovered for at least twenty-four hours, and

weigh dish and contents.


at intervals until there
is

Result?

Continue weighing
loss.

no further
is
it

Calculate the

per cent

of

loss.

What

that

escapes?

Record

your results systematically, as in Experiment VI. c. In a small beaker place a piece of potassium hydroxide,

and leave

it

exposed to the

air at least

an hour.

Result?

PER CENT OF WATER OF CRYSTALLIZATION. 29


d. Weigh an evaporating dish or a watch glass carefully, and then weigh into it accurately about 5 grams anhydrous

calcium chloride.

and weigh

What

Let stand at least twenty-four hours, Record the weighings as in 6. again. do these substances absorb from the air?
Results?

EXPERIMENT
Apparatus.
stand.
Materials.
cally
a.

XIX.

PER CENT OF WATER OF CRYSTALLIZATION.


Evaporating
dish,

balances, wire gauze, ring


(not plaster of Paris),
.

Powdered gypsum

chemi-

pure barium chloride (the hydrate)

dry),

Weigh your evaporating dish (be sure it and into it weigh accurately about

is

clean

and

powdered gypsum. taken, and record it. 6. Heat the evaporating dish on a clean wire gauze Then for ten minutes with the hottest Bunsen flame. Now let the dish cool, weigh it, and record the result. heat the dish again for five minutes, let it cool, and deter" constant mine the weight. Continue until you have
finely

3 grams of Get the exact weight of the

gypsum

weight."
c.

Record your

results thus:'

Grams.

Wt.

of evaporating dish

+ gypsum
alone

.'. Wt. of gypsum taken Wt. of evaporating dish

+ calcium sulphate =
alone

.'.Weight of water found = .'. Per cent of water in gypsum

30

LABORATORY EXERCISES.

d. Weigh into the evaporating dish, accurately, about 3 grams of pure, powdered barium chloride. Place the evaporating dish on a wire gauze about 4 inches (1 dm.)

above the top

of a

Bunsen

flame.

Heat the dish

for
it
c,

ten minutes, then let it cool, and weigh it. Heat Record the results as in again, to constant weight. and calculate the per cent of water driven off.

EXPERIMENT XX.
DEFINITE PROPORTIONS.
Apparatus.
glass.

Evaporating dishes, beaker, balances, watch

Materials.
a.

Sodium bicarbonate,

dilute

hydrochloric acid.

Weigh your evaporating dish carefully, and then weigh into it accurately about 5 grams of sodium bicarTransfer the bicarbonate without loss to a beaker covered with a watch glass; then add the dilute When adding acid hydrochloric acid a little at a time.
bonate.

draw the watch


let it

glass a little to

one

side;

at other times

cover the beaker.

6. The effervescence (foaming) is due to the escape of carbon dioxide gas. When all the solid has dissolved, add a drop or two more of the acid, to be sure no bicarbonate remains then pour the solution into the weighed
;

evaporating dish. With 5 c.c. water, wash what has spattered on the watch glass into the beaker, and with this water rinse what adheres to the beaker into the

evaporating dish. Rinse the beaker with 5 c.c. more water, and add the rinsings to the evaporating dish.

DEFINITE PROPORTIONS.
c.

31

Evaporate the solution to dryness, on a water bath

or a steam bath, if possible; otherwise, on a wire gauze. If you use wire gauze take great care to avoid spattering
either the solution or the solid

which remains after the


considerable

water
begins,
cool;

has

boiled

away.

If

remove the flame

for a

moment and
gently.

let

spattering the dish

then apply the flame again

Keep flame in

constant motion at the end of the process. When the solid in the dish is perfectly dry, let the dish cool to the temperature of the room. Then weigh it
accurately.
d.

Heat to constant weight. Record your results thus


:

Grams.

Wt.

of evaporating dish
,,

+ sodium bicarbonate
alone

= =

.*. Wt. of bicarbonate used Wt. of evaporating dish + sodium

chloride

alone
.'.

Wt.

of

sodium chloride formed

Get the simplest ratio between the amount of bicarbonate taken and that of sodium chloride obtained as
follows
:

Wt.

of bicarbonate

Wt.

of

sodium chloride

::

x.

Calculate the value of x to two decimal places, x = ? the preceding operations, weighing out e. Repeat If the accurately about 8 grams sodium bicarbonate. volume of the solution is too great to go into the evaporating dish

evaporate part of the water and then add the remainder of the solution. Be sure to rinse.
all at once,

32

LABORATORY EXERCISES.

sodium chloride as
clusion?

Calculate the ratio between sodium bicarbonate and before. Compare the ratios. Con-

EXPERIMENT
CHLORINE.

XXI.

If you inhaling much chlorine. smell ammonia If the gas cautiously. it, a few of into the ammonia room, sprinkle drops gets

Caution.

Avoid

have inhaled

water upon your table.


Apparatus.
stopper,
cover.

100

c.c. flask,

ring stand, wire gauze, one-holed

two right-angled tubes (one with long arm), rubber

connector, collecting bottle, test tubes, perforated cardboard


Materials. Manganese dioxide (in lumps), concentrated hydrochloric acid, white paper, red cheese cloth, litmus solution,

indigo solution, potassium chlorate, ink, printed paper.

on a wire gauze in a ring provided with a one-holed stopper and a delivery tube bent twice at right angles. The double bend is produced by joining two right-angle tubes by means of a rubber connector. The second right-angle tube is turned down; its end should be 2 to 3 cm. above the table.
a.

Support a 100

c.c. flask

stand.

The

flask

is

b.

Put into the

flask half a test


c.c.

tube of manganese
concentrated hydro-

dioxide in small lumps, add 20 chloric acid,- and attach stopper

Warm
mouth
bottle
is

and delivery tube. the flask gently, and fill a dry bottle, turned While the up, with the resulting chlorine gas.
being
filled

keep

it

covered with a piece of card-

CHLORINE.

33

You may know when


chlorine to the top;
will help
c.

board; the cardboard has a hole for the delivery tube. the bottle is full by the rise of

white paper held behind the bottle

you.

Stopper the bottle when it is full, and fill two dry test tubes with the gas. Then pass the gas for five minutes into 15 c.c. cold water in a test tube. This
gives chlorine water. When you are through, disconnect the apparatus at once, and wash the remaining manganese dioxide twice

with water.
d.

What

is

to a test tube of

the color of the gas? Apply a lighted match it. Does the gas burn? Support com-

bustion?
into the bottle of the gas a small piece (2 cm. of square) dry red cheese cloth, a wet piece of the same, a of piece paper containing print, and a paper with ink
e.

Put

Leave ten to fifteen minutes. Results? Put 5 c.c. of the solution of chlorine made in c upon /. 1 sq. cm. of the colored cloth in a test tube. Upon paper with both print and ink marks on it. Results? What seems to be necessary in order that chlorine may
marks.
bleach?
g.

close the

Into a test tube of the gas pour 5 c.c. cold water, mouth of the test tube tightly with the thumb,
vigorously.

and shake
Result?
h.

Remove thumb under

water.

Explain.
1 c.c. dilute

To

litmus solution, add chlorine water

you get a decided change. Explain result. ReResult? peat, using indigo solution instead of litmus. i. An easy way to make a solution of chlorine is to
until

treat about 1

gram

of potassium chlorate with 5 c.c.

34

LABORATORY EXERCISES.
is

gently.

concentrated hydrochloric acid. If action When the effervescence is rapid,


cold water.

slow,

warm
c.c.

add

10

EXPERIMENT

XXII.

HYDROGEN CHLORIDE.
Apparatus.
Materials..

Same

as in

Experiment XXI.
filings,

Sodium

chloride,

concentrated sulphuric acid,


silver nitrate solution,

red and blue litmus paper, iron

ammonium

hydroxide solution, dilute hydrochloric acid, sodium chloride solution, calcium chloride solution.

with stopper and delivery tube Experiment XXI, put 5 to 7 c.c. water, and add Result? carefully 20 c.c. concentrated sulphuric acid. In diluting sulphuric acid always pour the Caution.
a.

Into a 100

c.c. flask

as in

acid into the water.


b. Cool the diluted acid by holding the flask in a stream of running water. When the acid is cold, put into it about 15 grams sodium chloride. c. Attach the stopper and the delivery tube, and

Warm place the flask on the wire gauze of a ring stand. with a small and fill a bottle with carefully flame, dry the gas, it is hydrogen chloride, as in Experiment
XXI,
b.

You may know

that the bottle

is

full

when white fumes

escape about the cardboard which covers the collecting bottle.


Fill,

also,

a dry test tube, and stopper both vessels.

HYDROGEN CHWRIDE.
d.

35

Test the gas at the end of the delivery tube with Results? strips of moistened red and blue litmus paper. Result? Blow your breath against the stream of gas.
Explain.

the end of the delivery tube come just to the water in a test tube. Note the appearWhile the ance of the water below the delivery tube. so that the test raise tube off is regularly, coming gas
e.

Now

let

surface of 5 c.c.

the end of the delivery tube is about 2 cm. below the water level. Do gas bubbles pass through the water?

Why?
tube
five
is

Lower the

test

at the surface,

and

tube again until the delivery let the gas run into the water

Is there any change in temperature? the delivery tube from the water and remove Finally Save the liquid. flame. the extinguish Lower the wire gauze so as to let the flask cool out of

minutes.

contact with the gauze. of gas under water. /. Open the test tube
Explain.

Result?

Hold a burning match in the bottle of the gas burn? Does it support combustion?
g.

gas.

Does

Test the liquid- obtained in e with red and blue litmus. Compare results with those given by the gas. Add a drop of the liquid to 2 c.c. water, and taste a drop held on a stirring rod. 'Result?
h.
i.

Pour some

of the liquid of e

upon

1 c.c.

iron filings

in a test tube.

Result?
is:

Does the gas burn?


FeCl 2 +?
1
c.c. silver

The equation
j.

Fe+2HCl

a few drops of the liquid of e to Result? nitrate solution in a test tube.

Add

The white

precipitate

is silver

chloride,

AgCl.

36

LABORATORY EXERCISES.
is:

The equation

AgN0

HC1
hydrochloric acid

silver nitrate

To the precipitate add an excess of ammonium hydroxide solution, close the test tube with the thumb, and
shake vigorously.
k.

Result?

using sodium chloride solution in place of Result? Write the equation. hydrochloric acid. I. Repeat j again with calcium chloride solution in

Repeat

j,

Results? Conclusion? Equation? place of the acid. ra. Note the white solid which separates when the
flask

becomes

cool.
4.

It

is

chiefly

sodium hydrogen

sulphate,

NaHSO

Write the equation.

EXPERIMENT

XXIII.

WEIGHT OF A LITER OF OXYGEN.


Apparatus.
glass

Hard-glass
pinch-clamp,

test

tube,

one-liter

bottle,

bent

tubes,

graduated cylinder, balances, large

beaker or bottle.
Materials.

Powdered, chemically pure potassium chlorate,


C.

dried at 120
a.

Water

at

room temperature.

A is a Fig. 97. be tube that can hard-glass slipped tightly over a rubber stopper. B is a liter bottle fitted with a twohole rubber stopper. The longer tube reaches almost to the bottom of B, and is connected by a rubber tube with D, which reaches to the bottom of C. The rubber tube
Set

up the apparatus shown


test

WEIGHT OF A LITER OF OXYGEN.

37

may

bottle

be closed by the pinch-clamp F. Almost fill the B with water having the temperature of the room

and then

fill the tubes B, F, D, with water by sucking at the lower end of D,

being removed.

Then

close the pinch-clamp. 6. Into the test tube

put about 5

c.c.

of

pow-

dered, chemically pure potassium chlorate; it must have been dried at 120 C. for at least an hour. Get the weight of test tube

FIG. 97.
it.

and chlorate
c.

accurately

on the balances, and record


is

See that the stopper mouth of B, and then slip

pressed securely into the carefully, but tightly, over

Now put about 50 c.c. water into C, raise its stopper. C so that the water in B and C are at the same level, open the pinch-clamp one minute, and then close it. Then put C down on the table. Take D carefully out of C and get the volume of the water in C; then pour
in place. Now open the water back into C, and put tube to the it the and the pinch-clamp, glass hang upon of end to the lower not allow of F. Do left get

above d. Heat the chlorate

the surface of the


flame.

water in C.

Why?

moving
into C.

When

beginning with a The evolved gas forces water from B C is about full, stop heating, and let A
in
gently,

Then raise B or C, as necescool to room temperature. in both the same (be sure levels water the to make sary,
to keep the lower end of

under water), close the rubber

38

LABORATORY EXERCISES.

tube with the pinch-clamp, and get the volume of the water in C. This, minus the original volume, equals the

volume

of gas collected in B.

Find the barometric height, correct it for the pressure of water vapor (see Appendix), and find the temperature of the gas. Finally, weigh A. e. Record your results thus
:

Grams.

Wt. Wt.
.'.

of test tube of test tube

+* contents at

first

contents afterward

= =

Wt.

of

oxygen
ex.

Vol. of oxygen

Temperature of oxygen Barometer height (corrected) .'. Volume of C. and 760 mm. at .'. Wt. of 1 1. C. and 760 mm. at

C.

mm.
ex.
g.

EXPERIMENT XXIV.
PROPERTIES OF ACIDS.
Apparatus.
Materials.
Stirring rod, test tubes or beakers. sulphuric, and tartaric acids;

Nitric,

litmus

paper, phenolphthalein solution.

very dilute solution of sulphuric acid by the concentrated acid to 10 c.c. adding water in a clean vessel. By means of a clean stirring rod bring a drop of this solution to the tongue. What is
a.

Make a

three drops of

its

taste?

Note.

Whenever you

taste a substance in this

way always

PROPERTIES OF ACIDS.

39

be sure that it is greatly diluted. Keep it in the mouth long enough to determine the taste definitely; then reject it.
6.

By means

of the stirring rod

it

must be washed

after every test

upon

bring a drop of the dilute acid of a red and blue litmus papers. Results? A solution

which turns neutral or blue litmus red is said to have an add reaction. To the dilute acid add a drop of phenolphthalein solution.

Result?

Litmus paper should not be wasted. One piece many tests, if you use only a drop of the liquid each time. A new place on the litmus paper must, of course, be used at every trial. To avoid mistakes by reason of substances which may have spilled upon the table, lay the litmus paper upon the bottom of a clean, inverted beaker.
Note.
will

do for

Try the same experiments Results? With tartaric acid.


c.

as in a
acid.

and b with nitric In the case of the

tartaric acid use the solution obtained

by heating a small

crystal with 5
d.

c.c.

water.

Results?
i, tell

From Experiment XXII,


is

what happens when


Gaseous product?

iron

treated with

hydrochloric acid.
tell

Write

the equation here.


dilute sulphuric acid.
dilute
,

From Experiment VIII


from zinc and

From Experiment X tell


magnesium and
sulphate
e.

are formed Write the equation. what products are formed from

what products

is

What

If magnesium sulphuric acid. the write equation. MgSO4 seems to be the common gaseous product

formed when metals act upon acids?

40

LABORATORY EXERCISES.

EXPERIMENT XXV.
PROPERTIES OF BASES.
Apparatus.
Materials.

Same
Solid

as in Experiment XXIV. sodium hydroxide, potassium hydroxide,


solution, litmus,

and calcium hydroxide, ammonium hydroxide


filter

paper, phenolphthalein solution.

a.

in 10 c.c. water.

Dissolve a small piece of sodium hydroxide, NaOH, Rub a drop of the solution between

the fingers.

Result? Dilute 3 drops of this with 5 c.c. water and taste the solution, using a stirring rod. Result? Find its effect upon blue and red litmus as in Experiment XXIV, 6. Result? Add a drop of phenolphthalein to it. Result? A solution which turns neutral or red litmus blue has an alkaline reaction.

b. Repeat a, using potassium hydroxide instead of sodium hydroxide. Results?


c.
4

Add
its

2 drops of
to 5
c.c.

ammonium
Note

NH OH,
and
d.

water.

hydroxide solution, taste of dilute solution

action on blue and red litmus and phenolphthalein.


,

Treat about 1 gram calcium hydroxide, Ca(OH) 2 or calcium oxide, CaO, with 10 c.c. water, stir one minute, and then filter. Examine the solution it is called
lime-water
as to taste, feel,

and action upon blue and red

litmus and phenolphthalein.

PROPERTIES OF SALTS.

41

EXPERIMENT XXVI.
PROPERTIES OF SALTS.
Apparatus.
Materials.

sulphate,

Same as in Experiment XXIV. Sodium chloride, ammonium nitrate, potassium sodium acetate, sodium carbonate, disodium hydro-

gen phosphate, phenolphthalein solution.


a. Treat about one cubic centimeter of sodium chloride, NaCl, in a test tube with 5 c.c. water. Test the solution with blue and red litmus as in Experiment XXIV, a and b. Results? Test it with phenolphthalein.

Result?

with b. Repeat a with ammonium nitrate, 4 N0 3 with sodium acetate, potassium sulphate, K2 S0 4
;
;

NH

NaC H
2

2.

Results?
;

Repeat a, using sodium carbonate, Na 2 CO 3 disodium hydrogen phosphate, NasHPC^. d. Arrange in a table the reactions of the substances you have examined with litmus in Experiments XXII, XXIV, XXV, and XXVI, thus:c.

FORMULA
OF SUBSTANCE.

42

LABORATORY EXERCISES.

What element is found in every acid? What two elements are found in every basic hydroxide? What element is not present, usually, in the saltSj i. e., the
substances studied in this experiment?

EXPERIMENT

XXVII.

NEUTRALIZATION.
Apparatus.
ring stand. Materials.

Evaporating

dish,

stirring

rod,

wire

gauze,

solution, dilute hydrochloric

Litmus solution and paper, sodium hydroxide and nitric acids.

a. To 5 c.c. ten per cent sodium hydroxide solution in an evaporating dish add 1 c.c. litmus solution; then add slowly dilute hydrochloric acid until the litmus

changes

color.

During the addition of acid, stir constantly with a glass If you get too much acid, add sodium hystirring rod.
droxide

by means

of the stirring rod until the color just

becomes blue again; then add a small drop of very dilute With care you can get the litmus to hydrochloric acid. assume a color intermediate between the red and the blue,
viz.:

a decided

lavender.

This

is

the color of neutral

litmus, and its formation shows that the basic properties of the sodium hydroxide solution have been neutralized

by the hydrochloric
b.

acid.

Put a drop of the solution upon red litmus, as in Experiment XXIV, 6; upon blue litmus. Result? c. Evaporate the solution carefully. At the end, when

NORMAL AND ACID

SALTS.

43

the water is nearly all off and spattering begins, heat with a small flame in constant motion. d. Examine the product obtained in c, noting its taste,
solubility in water,

and the reaction


is

of the solution

with

litmus.

Results?

The substance obtained


salt.
e.

sodium

chloride, or

common

? + ? Complete the equation, NaOH+HCl Repeat a, 6, c, and d, using dilute nitric acid instead

of hydrochloric acid.
If

Results?

the product has the formula

NaN0
?

3,

complete the

equation,

NaOH + HN0

EXPERIMENT

XXVIII.
SALTS.

NORMAL AND ACID

Two evaporating dishes, burette, test tube, Apparatus. rubber band, filter paper. Pure concentrated sulphuric acid, ten per cent Materials.
potassium hydroxide solution, phenolphthalein.
a.

to

mark

Put a small rubber band evenly around a test tube Do not change the off 5 c.c. (see Experiment I).

position of the rubber during the experiment. b. Dilute 15 c.c. pure concentrated sulphuric acid

by

pouring
rod,

it

into 35 c.c. water; stir the mixture with a glass

and cool it as in Experiment XXII, b. Hold your marked test tube vertically and pour in the See that the upper edge of dilute acid up to the mark.
the rubber
is

just at the lower level of the meniscus,

i.

e.,

44

LABORATORY EXERCISES.

the curved surface of the liquid. Pour the 5 c.c. of acid into an evaporating dish, rinse the test tube with 5 c.c. of water, and add the rinsings to the acid in the dish.

Note what part


the resulting 10

of

c.c. of liquid, for

your evaporating dish is occupied by comparison in e of this

experiment.
c.

Add

to the evaporating dish 3 drops of

phenolphthalein solution.
a burette with ten per cent potassium hydroxide The burette is best fitted with rubber and a solution. If a glass stopglass tip controlled by a pinch-clamp.
Fill

used see that it is well lubricated with vaseline. Support the burette in a clamp, put under it a beaker, and let the liquid run out until the part of the burette below the clamp is filled with liquid. Return the liquid which ran out to the burette. Read the level of the
cock
is

liquid exactly to tenths of a cubic centimeter, having your eye in the same horizontal plane with the bottom of the meniscus. Record this reading.
d.

Open the clamp

of the burette carefully,

and

let

the potassium hydroxide solution fall drop by drop into the evaporating dish of dilute acid. Stir constantly.

Get the solution exactly neutral, or one drop of alkali in excess.

at

any

rate have only

Read the burette


e.

again.

How much

alkali
c.c.,

Evaporate the solution to about 12


Result?

was used? and let it

cool thoroughly.
/.

Repeat
i. e.,

b, c,

acid,

10

c.c.,

and d with twice the quantity of dilute and exactly as much potassium hydroxResult?
let
'it

ide as

was used

in d.

Test solution with litmus.


resulting solution to 5
g.

Evaporate the
Result.
e

c.c.,

and

cool.

Dry

the solid substance obtained in

between

filter

NORMAL AND ACID SALTS CONTINUED.


papers.

45

What

is

the

general shape

of

the

crystals?

Heat one in a dry test tube. Has it crystal water? Treat some of the crystals with 1 to 2 c.c. water in a test tube. Are they easily soluble? What is the reaction of
the solution to litmus?
h.

Its taste?
g.

Treat the crystals obtained in / as directed in Results? Are the crystals in the two cases alike?
.

How many

salts

does sulphuric acid form with potasthis experiment?

sium hydroxide, according to

EXPERIMENT XXIX.
NORMAL AND
Apparatus.
Materials.

ACID SALTS CONTINUED.

Same as in Experiment XXVIII. Concentrated pure hydrochloric

acid,

ten per

cent potassium hydroxide solution, phenolphthalein.

In the marked test tube (see Experiment XXVIII, measure out 5 c.c. concentrated hydrochloric acid, a) this acid into an evaporating dish, and rinse the tube put
a.

of water, as in Experiment XXVIII, 6. Add with ten cent and neutralize per phenolphthalein, potassium hydroxide from the burette. Note the amount of

with 5

c.c.

alkali used.
6. Evaporate the neutral solution to dryness. Finally, heat the evaporating dish until no fumes of any kind come off, and even the crackling sound decrepitation

practically ceases.

Let the dish cool thoroughly. c. Examine the product, noting its solubility in water, the taste of the solution, and its reaction with litmus.

46

LABORATORY EXERCISES.

d. Repeat a, b, and c, with the same amount of alkali, but with twice the quantity, i. e., 10 c.c., of hydrochloric

acid.

Be
e.

sure to evaporate as directed in b. Compare results with those obtained in


salts

c.

How

many

do you get hydrochloric acid to form with

potassium hydroxide?

EXPERIMENT XXX.
IONIZATION.
Apparatus.
Materials.

Test tubes, mortar and pestle. Solutions of silver nitrate, potassium chloride,

potassium chlorate, sodium hydroxide, and potassium ferrocyanide; solid ferrous sulphate,
a.

sodium bicarbonate, and tartaric

acid.

Experiment XV,

Double decomposition between two salts. Review In a, and write the equation here.

the double decomposition reactions of acids, bases, salts, and water, the materials that react may be classified under
the following heads:
1.

Metals,

3. 4.

2.

Hydrogen,

Acid radical, Hydroxyl.

XV,

Classify the materials of the a, under these heads.

two

salts of

Experiment

Take 2
tubes.
solution.

c.c. silver

nitrate solution in each of

two

test

To one add
(

a few drops of potassium chloride Write the equation, indicating the precipitate
j).

by an arrow
this case also.

Classify the materials that react in


is

Why

a precipitate formed?

ION I Z AT ION.

47

the other tube of silver nitrate add some pure potassium chlorate solution. Result? Write the equilibrium equation (^ZZ!) for the reaction. Why is there

To

no precipitate? Of what radical is the chlorine a part? b. Double decomposition between salts and bases. Powder about 1 c.c. of ferrous sulphate, FeS0 4 and shake it with 5 c.c. of water. Pour off the solution, and add to it a few drops of sodium hydroxide solution. Result?
,

If

the precipitate has the formula Fe(OH) 2 write the equation. Classify the materials that react in this case.
,

Treat about 3 c.c. of potassium ferrocyanide solution, with a few drops of sodium hydroxide solu6 tion. Result? Why is Fe(OH) 2 not precipitated as before? Of what radical is the iron a part?

K Fe(CN)
4

c. Double decomposition between salts and acids. Review Experiments XV, b, XX, a, and XXII, m, and Use the proper arrows for rewrite the equations here.

Classify, as in a, the precipitates or escaping gases. materials that react in the case of salts and acids.

Grind together about 1 c.c. each of sodium bicarbonate and tartaric acid in a dry mortar. Is there any evidence Now add water, and account for the of a reaction?
difference.
d.

Write the equation

(c/.

280 of

text).

Double decomposition between acids and bases. Review Experiments XXVII to XXIX. Write here
the equations involved. Classify the materials of acids and bases that react by double decomposition. What
tion?

always formed in neutralizaWhat to produce it? becomes of the other two? For which materials do we

one substance (not

class) is

What

materials

unite

test

with indicators

like

litmus and phenolphthalein?

48

LABORATORY EXERCISES.

EXPERIMENT XXXI.
HYDROLYSIS AND REPLACEMENT.
Litmus paper, antimony chloride, bismuth iron nails (brads), copper turnings, and zinc (strips or nitrate,
Materials.

granulated);
tions of

concentrated hydrochloric and nitric acids; soluchloride, cupric sulphate,

aluminum

mercurous

nitrate,

and
a.

silver nitrate.

To
,

a small amount (half a


c.c.

SbCl 3

add 5
If

Result?

c.c.) of antimony chloride, shake the two together. and water, the product first formed is antimony

OH
dihydroxy chloride,
b.

SbOH,
Cl

write the equation.

the precipitate add concentrated hydrochloric a drop at a time, warming after each drop. Result? acid, If the solution contains antimony chloride, SbCl 3 write

To

the equation. Rec. Add the solution obtained in b to 50 c.c. water. sult? Add concentrated hydrochloric acid again. Result?
d.

Compare the equations

of a

and

b.

Write one of

them, using, arrow ^ZI


chiefly

instead of the equality sign, the double In which direction does the reaction go
excess of water
is

when an

used?

When an

excess

of acid is used?

Repeat the experiment with bismuth nifrate, Bi(NO 3 ) 3 and water, and use concentrated nitric acid instead of hydrochloric acid. Write the equation.
e.
,

NITROGEN.
/.

49

Recall Experiment

XXVI

for the reaction of salt

with litmus. For the reaction of sodium carbonate. Try the action of aluminum chloride solution with red

and blue litmus paper.


NaCl
2

Complete the equations,

+HOH
3

^=? +
7 ? ?

Na C0 +2HOH
A1C1,

+3HOH 7

+? +?

For which of these three reactions do you get no evidence Of what reaction is from the behavior with litmus?

Why hydrolysis the reverse? compared with its reverse?


g.

is

it

so

incomplete as

Replacement.

in a test tube
let

add

To 5 c.c. cupric sulphate solution several small iron nails (brads) and
Result?

stand over night.

in the color of the solution.

What change has occurred What is the precipitate?


nitrate

Write the equation. Repeat, using mercurous

(HgNO

3)

solution

with copper turnings. Equation? Repeat again, with strips of zinc, or granulated zinc, and silver nitrate solution. Result and equation? Compare the results with the action of a metal on an
acid, as in

Experiment VIII.

EXPERIMENT XXXII.
NITROGEN.
Apparatus.
100
c.c.

flask,

wire gauze, ring stand, clamp,

bottle. stopper, delivery tube, pneumatic trough, collecting ammonium chloride, 2 Sodium nitrite, Materials.

NaN0

NH C1.
4

50

LABORATORY EXERCISES.

a. Support a flask by means of a clamp about its neck, and place under it the wire gauze. Put into the flask 5 c.c. powdered sodium nitrite, 5 c.c. ammonium chloride, and 50 c.c. water. Attach the stopper and delivery tube; the delivery tube extends to a pneumatic trough containing water and an inverted collecting bottle full of water.
6.

Have ready your evaporating


If at

dish full of cold water.

Heat the

flask gently until a regular

stream of gas escapes.

but not too rapid any time during the heating

the evolution of gas (nitrogen) becomes violent, remove the delivery tube from the water, take away the flame

and wire gauze, and bring the evaporating dish of cold water up over the bottom of the flask. Let two test tubes of gas escape (why?) then fill the bottle with it.
;

c.

Determine the odor and color

of the gas, also its

relation to combustion.

Write the equations for the stages of the


also the complete equation,

reaction;

EXPERIMENT

XXXIII.

AMMONIA.
Mortar and pestle, stirring rod, test tubes, Apparatus. 100 c.c. flask, stopper, two right-angle tubes, collecting bottles,
gauze.
Materials.

Glue,
chloride,

quicklime,

litmus,
nitrate,

hydrochloric

acid,

ammonium

sulphate, sodium hydroxide solution, potassium hydroxide solution.

ammonium

ammonium

AMMONIA.
a.

51

Mix

in a

mortar about one half gram glue and 2

grams quicklime, and heat the mixture in a test tube. Hold in the mouth of the tube, without touching the
tube, a piece of moist blue litmus paper.

Red

litmus

glass rod which has been dipped into conpaper. centrated hydrochloric acid. Results? Note odor.

What is it? b. To about one


test

half

gram ammonium

chloride in a

tube add 2

c.c.

ten per cent sodium hydroxide,

solution,

litmus?
acid?

On

and warm gently. Odor? Effect of gas on a rod wet with concentrated hydrochloric
b,

using ammonium nitrate and sodium Results? Use ammonium sulphate and ten per cent potassium hydroxide solution. Results? The gas formed in the above cases is ammonia, 3
c.

Repeat

hydroxide solution.

NH

mix 10 grams powdered ammonium chloride and 20 grams powdered quicklime. Odor? Support the flask on wire gauze and attach the stopper and a delivery tube bent twice at right angles
d.

In a 100

c.c.

flask

Experiment XXI, a). Have the second rightangled tube turned upward. On a small ring fastened high up on the ring stand, lay a piece of cardboard with
(see

a small hole in

it;

and invert over the

through the hole pass the delivery tube, delivery tube the dry receiver (bottle)
is full

intended to collect the ammonia. When the bottle e. Heat very gently.
test

of gas,

this

nose) Now turn the end of the Fill three bottles with the gas. the surface delivery tube down, so that it just touches of 10 c.c. water in a test tube.

cover

by waving air from the bottle toward the it and place it mouth down upon the table.

52

LABORATORY EXERCISES.

cm.

After a minute raise the test tube carefully about 2 Do the bubbles of ammonia rise to the surface of

Why? Lower the test tube again until the tube delivery just touches the water, and continue the flask Remove the heating gently three minutes. test tube; and then extinguish the flame. Let the flask cool not in contact with the wire gauze or any conthe water?
ductor.
/.

Why?
in the

Did you notice any change

water of the test tube?


g.

Explain. the method of collecting the gas compare its Is there any evidence specific gravity with that of air. of water in the generating flask?

temperature of the Save this liquid.

From

h.

Test the gas in the


of receiver

first

keep mouth

down.

receiver with litmus paper Test relation of this gas

to combustion.

Results?

Thrust up into the receiver a glass rod which has been dipped in concentrated nitric acid. Results? The smoke is ammonium nitrate, Write the 4 NO 3

NH

equation. i. Place the second bottle


water.
j.

mouth downward

in a

pan

of

Explain. the bottom and sides of a clean, dry bottle (having a mouth of the same size as that of the third bottle of ammonia) by moving it quickly to and fro in the

Result?

Warm

Bunsen flame;

put

into

it

five

drops

concentrated

bottle of hydrohydrochloric acid, chloric acid gas thus obtained, the bottle of ammonia. Hold the mouths of the bottles firmly together and re-

and place over the

verse their positions, so that the ammonia bottle below the other. Results? What is the product?
k.

is

Examine the solution

of

ammonia made

in

e.

NITRIC ACID.

53

What effect has it upon litmus? Hold a piece of moist red litmus about 2 cm. above the solution. Result? Explain. Put 5 c.c. of the solution into a beaker, note the
odor,

and

let

beaker stand for twenty-four hours.


Inference?

Is the

odor

as strong as before?

1. Put about 5 c.c. of the ammonia solution of e into an evaporating dish, and boil it gently for five minutes. Compare odor after boiling with that of some of the

original solution.

m. Heat a small amount of ammonium chloride for some time on a piece of porcelain or on platinum. Result? Write the equations for the reactions which took place in 6, c, d, and e, as double decomposition equations; then show the dissociation of ammonium hydroxide.
n.

EXPERIMENT XXXIV.
NITRIC ACID.
100 c.c. flask, cork stopper, delivery tube (in Apparatus. one piece), test tube, beaker, wire gauze, ring stand. Materials. Potassium nitrate, concentrated sulphuric and
nitric acids,

white

silk thread,

indigo solution, ferrous

ammo-

nium sulphate
a.

or ferrous sulphate,

and copper

nitrate.

Use apparatus
put 5
g.

of

Experiment XI,

Fig. 96.

Into the

potassium nitrate and 10 c.c. concentrated sulphuric acid. Attach the stopper and the delivery tube. The delivery tube must be in one piece without Put the end of the delivery tube rubber connections.
flask

54

LABORATORY EXERCISES.
The

test

into a test tube resting in a beaker of cold water. tube will serve as a condenser.
b.

gradually over the wire gauze. Keep the end of the delivery tube out of the liquid which condenses in the test tube. When no more liquid distills over, remove the de-

Warm

the

flask

Result?

Color of fumes?

livery tube.

Only then remove the flame.


collected
is

The

liquid

nitric

acid.

Complete the

equation,

KN0 +H S0
3

KHS0 +?
4

What
c.

is the color of the acid? Let the flask cool thoroughly.

Result?

Name

the

crystalline product. resulting solution into the sink.


d.

Finally, add water and pour the

Add

1 c.c.

of the nitric acid

you have made to

1 c.c.

of water,

and

test the action of a

drop (use the glass rod)

upon

litmus.

Result?

yarn, and

Into your diluted acid put a piece of white woolen warm gently. Remove the yarn. How has it

changed?

To
e.

1 c.c. of

your dilute acid add a few drops of indigo

solution.

Result?

Will
/.

What color does your undiluted acid give to the skin? ammonium hydroxide remove the stain? Treat about 2 c.c. of ferrous ammonium sulphate

or of ferrous sulphate in a test tube with 15 c.c. water and shake vigorously. Take 5 c.c. of this solution in a test tube, add two drops of dilute nitric acid, incline

the tube at an angle of about forty-five degrees, and pour about 3 c.c. concentrated sulphuric acid down the side of

NITRITES.
tube.

55

Describe what takes place where the conis below, meets the solution. g. Repeat /, using a solution of potassium nitrate instead of nitric acid. Result? Repeat again with Result? cupric nitrate instead of the acid. h. If the test just tried is a general one for all nitrates,
centrated acid, which

how would you proceed

to test a solution for the presence

of a nitrate or nitric acid?

EXPERIMENT XXXV.
NITRITES.
Apparatus.
Materials.

Iron dish, stout iron wire, beaker, test tubes.

Potassium

nitrate, lead, filter paper, dilute sul-

phuric acid.

Melt together in a shallow iron dish 10 grams potassium nitrate, KNO 3 with about 20 grams of lead. Keep the mixture at red heat, and stir twenty minutes
a.
,

with a stout iron wire or a nail held in iron tongs. 6. When the mass is cool add 20 c.c. water, heat to
boiling for a few minutes, take out the unused lead,

and

then

filter.

The residue on the filter is lead oxide, PbO. Its color? The filtrate contains potassium nitrite, KNO 2 and unchanged nitrate. The reaction is a reduction of potassium nitrate by lead, as is shown in the equation, KNO 2 + PbO. KN0 3 + Pb
,

Treat the solution of potassium nitrite from b with dilute sulphuric acid. Result? Treat some potasc.

56

LABORATORY EXERCISES.
test

acid,

slum nitrate solution in a and compare results.

tube with dilute sulphuric


trioxide,

d. The brown gas is nitrogen shown by the equations,

NO
2

3,

formed as

KN0 + H SO 2 HN0
2
2

KHSO + HNO
4

2.

+H 0.
2

EXPERIMENT XXXVI.
NITROGEN TETROXIDE.
Apparatus.
Material.
a.

Test tubes, doubly bent delivery tube.

Powdered lead

nitrate,

Pb(N0

3) 2.

Heat 5 grams powdered lead

nitrate carefully in a

test

tube (use a holder), keeping the tube in constant Result? motion. When the tube is full of gas, attach a stopper and a Fill delivery tube with its longer arm turned down.

a dry test tube with the evolved gas by displacement of


air.
b.

leave

Invert the test tube of gas in a beaker of water, and it a few minutes. Result? Test the residual
it.

gas with a pine splinter having a spark on the end of Result?


c.

The brown gas


tetr oxide,
is,

is
2

nitrogen dioxide,
4.

NO

2,

mixed with

nitrogen

The equation

Pb(N0
d.

3) 2

PbO+N O
2

4 (t.

e.,

NO )+O.
2

The

lead oxide in the test tube

may

nearly

all

be

NITRIC OXIDE.
removed by adding to the cold tube and heating carefully.

57
dilute nitric acid

EXPERIMENT XXXVII.
NITRIC OXIDE.
Apparatus. Generating bottle (250 c.c.), two stoppers (one two-holed and one one-holed), funnel tube, delivery tubes,

pneumatic trough, wide-mouth collecting


glass covers.

bottles,

cardboard or
nitric

Materials. Copper (granulated or turnings), ferrous sulphate, splinter of pine, red phosphorus.
a.

acid,

a generating bottle (250 c.c.) put enough granulated copper to cover the bottom. Attach stopper containing funnel tube and delivery tube. Add through
Into
the funnel tube

enough

dilute nitric acid to

immerse the

lower end of the tube, and then concentrated acid, as

The gas produced is necessary, to give brisk action. is the acid too concentrated, connitric oxide, NO. //
siderable nitrogen tetroxide is produced.
b.

Fill

to the air.
in

a bottle over water with the gas, and expose it Result? From the result tell why the gas
c.c.

c.

the generating flask was originally brown. Pass the gas about three minutes into 10

concenResult?
the gas
it

trated ferrous sulphate solution in a test tube. Save the solution for g.
d.

Collect a second and a third bottle

full of

over water.

Cover one

of the bottles,

remove
it

from

the water, turn it mout'h upward, and put into Result? splinter.

a lighted

58
e.

LABORATORY EXERCISES.

Repeat d with the last bottle of the gas, using a deflagrating spoon containing briskly burning red phosphorus,

instead of the splinter. Compare results. Is nitric oxide a supporter of combustion, or not?

/. Attach to the test tube of solution from c a oneholed stopper and a delivery tube. Warm gently and collect the evolved gas over water in a test tube. Expose the gas to the air. Result? Conclusion?

The brown liquid obtained in c contains a compound of ferrous sulphate and nitric oxide (FeSO 4 .NO).
See Experiment
ring of this
nitrates.
g. Pour 25 c.c. of the solution (its color?) left in the generating flask into a beaker, add any unused copper, and let the beaker stand (in a gas chamber if possible) until all action ceases. There should be an excess of

XXXIV,

/,

compound was used

where the formation of a brown as a test for nitric acid and the

Peur the liquid into an evaporating dish, and copper. evaporate on a wire gauze to about 10 c.c. Dip into the liquid a glass rod, and see if the liquid which sticks to the rod will solidify on cooling. If so, let the dish cool
;

if

not, evaporate off

about 2

c.c.

more, and try again.

Result?

The substance obtained is cupric nitrate, Cu(N0 3 ) 2 Write the partial and complete equations.

NITROUS OXIDE.

59

EXPERIMENT

XXXVIII.

NITROUS OXIDE.
Test tubes, stopper, delivery tube, pneumatic Apparatus. trough, clamp, ring stand, collecting bottle. Materials. Ammonium nitrate, pine splinter.
a. Into a test tube provided with stopper and delivery tube put about 10 grams ammonium nitrate, and fasten the test tube by a clamp to the ring stand. The test

tube should be inclined at an angle of about forty-five


degrees.

Invert a bottle of water (best warm) in the pneumatic trough, but do not put the delivery tube into the water
until
b.
c.

tube gently with a moving flame. Result? Result? Warm of gas is evolved, hold over the stream When a steady a cold and dry beaker. What tube end of the delivery
test

Heat the

more.

collects in it?

put the end of the delivery tube into the pneumatic trough, and fill the collecting bottle with the gas. The gas is nitrous oxide, N 2 0. Write the equation. Set the bottle of gas mouth upward and covered upon
c.

Now

the table, and then


Note.

fill

a test tube with the gas.

Be

sure

to

take the delivery tube out of the water before

you remove
d.

the flame.

the test tube of gas add 5 c.c. cold water, close the tube tightly with the thumb, and shake vigorously. the tube under water. Result?

To

Open

60
e.

LABORATORY EXERCISES.
What

into

Insert is the odor of the gas in the bottle? a pine splinter with a glowing tip. Result? What gas resembles nitrous oxide in its vigorous supit

port of combustion?

EXPERIMENT XXXIX.
PHYSICAL PROPERTIES OF SULPHUR.
Apparatus.
beaker.
Materials.

Test

tubes,
roll

filter,

funnel,

evaporating

dish,

Powdered

sulphur, carbon disulphide.

a. Test the solubility of sulphur as follows: In a test tube shake 1 c.c. powdered roll sulphur with 5 c.c. water; filter, and evaporate the nitrate in an evaporating dish. Result? Conclusion? What is the odor of sulphur? Its taste? 6. Treat not more than 1 c.c. powdered sulphur in a test tube with 5 c.c. carbon disulphide.

Carbon disulphide is inflammable. Do near a flame. Close the test tube with the thumb, and shake it Result? Pour the contents of the tube thoroughly.
Caution.
not bring
it

into a small beaker,


(not

in

your

set this aside in a gas chamber cupboard) until the carbon disulphide

and

evaporates.
crystals?
c.

Result?

What

is

the shape of the larger


sulphur, hold
it

Fill

a test tube one-third

full of

in-

clined at
it

an angle

carefully.

about forty-five degrees, and heat Note the changes through which the sulof
raise its temperature.

phur passes as you

CHEMICAL PROPERTIES OF SULPHUR.


What
sulphur?
is

61

the color of the liquid formed by melting the


Is it viscous

(thick)

or limpid (thin;

easily

poured)? product? 114 C.


d.

Pour a drop
Is
it

of

it

into water.

Color of the

hard or soft?

Sulphur melts at about

What change
it

does the sulphur undergo


until

when you

heat

further?

Tilt the test tube to an almost horizontal

position

from time to time

you find

the point at

cannot be poured. Then continue heating, and notice that the sulphur becomes limpid again.

which

the liquid

that boiling

You will know Finally, heat the sulphur to boiling. is taking place when you see the dark brown

liquid condensing upon the upper (cooler) parts of the tube. Sulphur boils at 446 to 448 C.

sulphur into a beaker of cold Is it hard or of the product? Color water. for several this Elastic or brittle? soft? weeks, Keep noting from day to day any changes that take place.
e.

Pour the

boiling

Result?

EXPERIMENT

XL.

CHEMICAL PROPERTIES OF SULPHUR.


Apparatus.
test tube.

Deflagrating spoon, 250

c.c.

bottle, cardboard,

Materials.
a.

Sulphur, blue litmus paper, powdered iron.

1 c.c. powdered sulphur in a deflagrating in the flame until it burns briskly, and it heat spoon, then put the spoon into a bottle of air. Keep the bottle covered with cardboard having a hole in it for the handle

Put about

of the spoon.

62

LABORATORY EXERCISES.

Let the sulphur burn as long as it will. Name the product of the combustion. What is its physical state? Its odor? Try its effect upon wet blue and red litmus
papers.

mortar 5.6 grams powdered iron and 3.2 grams powdered sulphur, and put the mixture into a test tube. Heat the lower portion of the tube for a
6.

Mix

in a

moment

in the Bunsen flame. Result? When action withdraw from the flame. Dethe test tube begins,

scribe all that takes place.


c.

When

the product
solid

is

cool,

break the test tube, and


It
is

remove the

lump.

Describe the product.


its

ferrous sulphide, FeS. Write the equation for


for

formation.

Save the

solid

Experiment XLI.

EXPERIMENT

XLI.

HYDROGEN SULPHIDE.
Apparatus.
Materials.

Test tubes, stopper, and delivery tube.


Ferrous sulphide from Experiment

XL;

dilute

sulphuric acid; solutions of cupric sulphate, barium chloride, lead nitrate, cadmium sulphate, sodium hydroxide, and litmus.

Note.
there
a.
is

Perform this experiment


a good draught.

in

a gas chamber, or where

ment

Treat the lump of ferrous sulphide made in ExperiXL with dilute sulphuric acid in a test tube. Result? The gas is hydrogen sulphide, Attach a 2 S.

stopper and delivery tube, and

fill

a test tube held

mouth

HYDROGEN SULPHIDE.
upward with the gas. Result? Note odor
Complete the equation,

63
test tube.

Apply a match to the


of

the

burning

gas.

Result?

H S+O
2

b.

Pass the hydrogen sulphide gas from the generating


c.c.

tube into 5

dilute cupric sulphate

(CuSO 4 )

solution

Continue about one minute. Now see that the delivery tube is clean, and pass the gas three or four minutes into 15 c.c. water in a test tube. Then wash out the generating tube thoroughly.
c.

in a test tube.

Result?

Filter the test tube of cupric sulphate into

which

you have passed hydrogen sulphide.


Conclusion?

Compare

the color

of the nitrate with that of the cupric sulphate taken.

The black

residue

is

cupric sulphide,

CuS.

Write

the equation for the action of hydrogen sulphide upon


cupric sulphate.

a few drops of the hydrogen sulphide solution Result? If lead nitrate solution, Pb(N0 3 ) 2 the insoluble product is lead sulphide, PbS, write the
d.

Add
c.c.

to 2

equation.

Repeat, using cadmium sulphate solution in place of Result? If the insoluble product is nitrate. cadmium sulphide, CdS, write the equation.
lead
e. Test the reaction of the hydrogen sulphide solution with red and blue litmus papers. Results? Conclusion? Add to the remainder of the hydrogen sulphide solution

c.c.

sodium hydroxide

solution.

The

solution

now

contains sodium sulphide,


/.

Na2 S. Write the equation. How would you make ammonium sulphide solution,
S?

(NH

4) 2

Write the equation.

64

LABORATORY EXERCISES.

EXPERIMENT

XLII.

SULPHUR DIOXIDE.
Apparatus.
rating dish. Materials.

100

c.c.

flask, ring stand,

wire gauze, stopper

and delivery tube, 2

collecting bottles, test tubes, beaker, evapo-

Granulated copper, concentrated sulphuric acid, red flower, red cheese cloth, crystals of cupric sulphate, dilute sulphuric acid, sodium hydroxide solution, litmus paper, concentrated nitric acid, potassium permanganate and potassium

dichromate solutions.
c.c. flask put about 5 grams copper and add concentrated sulphuric acid. Support the flask in a ring stand, upon wire gauze, and attach a stopper

a.

In a 100

25

c.c.

and a doubly bent delivery tube reaching almost to the


table.
b.

Heat the

flask carefully.

When

brisk effervescence

Collect 2 bottles of the gas begins, moderate the heat. as you did chlorine in Experiment XXI, 6. Tell when each bottle is full by the odor. Stopper the bottles. Collect, also, a test tube of the gas and put it, mouth

down, into a beaker

of water.

Explain the

result.

Wave
Odor?

little

of the escaping gas

toward the nose.

sulphur dioxide, SCV of the delivery tube just at the surface of 10 c.c. water in a test tube. When the gas is coming off freely, raise the test tube about 1 cm. What evidence is there that the gas is Lower the test tube dissolving?
is
c.

The gas

Put the end

to its former position

and keep it there

five

minutes.

Then

SULPHUR DIOXIDE.

65

remove the delivery tube from the water, extinguish the flame, and let the generating flask cool hi position, out
of contact with the wire gauze.

Stopper the test tube containing the solution of the gas, and keep it. d. Into one bottle of sulphur dioxide gas put a few
petals of some red flower, e. g., a carnation; also a small piece of wet, red cloth such as you used with chlorine
in

Experiment XXI,

e.

Results?

Test the action of sulphur dioxide upon blue litmus Result? paper.
e.

To

the second bottle of sulphur dioxide add 4 drops

of concentrated nitric acid, stopper the bottle, and shake it. Results? Add 5 c.c. water, stopper once more,

shake, and pour the liquid into a test tube.

Save this for

Experiment XLIV,
f.

c.

Note the

solution

made

in

taste of a drop of the sulphur dioxide What is the action of 1 c.c. of it c.

upon 1 c.c. potassium permanganate Repeat with potassium dichromate

solution (KMnO,i)? solution instead of

potassium permanganate. Result? Sulphur dioxide solution contains

sulphurous

acid,

H S0
2

3.

g.

Neutralize the remainder of the sulphurous acid in

an evaporating dish with 10 per cent sodium hydroxide The resulting subsolution and evaporate to dryness. stance is sodium sulphite, Na^SOa. Describe it.

Complete the equation,


2
h.

NaOH+H SO
2

Treat the sodium sulphite in a test tube with a

little

dilute sulphuric acid,

and warm.

Note the odor.

66
The
sulphite

LABORATORY EXERCISES.
is

decomposed by the acid thus:

Na2 S0 4 +H SO
2

(i. e.,

SO2 +H2 O).

the generating flask is cold, add to it 25 c.c. water, shake carefully, and heat the flask cautiously over wire gauze. Filter the resulting liquid. What is the color
i.

When

of
let

the
it

filtrate?

Concentrate

cool.

Result?
4.

it to about 15 c.c., and Compare the product with blue

vitriol,

CuSO

H O. Complete the equation, Cu+H S0


2

EXPERIMENT

XLIII.

SULPHURIC ACID.
Apparatus.
balances.
Materials.
File or blue paraffin pencil, test tube, beaker,

Concentrated sulphuric acid, sugar, cotton,

cloth,

paper, splinter.
a.

By means
c.c.

of a

file

or a blue paraffin pencil

mark

off

on a clean, dry test tube, set the tube in a clean beaker, and get the weight of both test tube and beaker together. Now fill the tube up to the mark with concentrated sulphuric acid, wipe off any acid adhering to the mouth of the test tube, and get the weight of acid
about 10

beaker

test tube.

Return the acid to the bottle, rinse the test tube, and dry it on the outside. Then fill the tube up to the mark with water, and get the weight of water + beaker + test
tube.

SULPHATES.
Record your
Wt. Wt.
*
.

67

results thus

Grams.
of test tube -f beaker
of test tube

+ sulphuric acid
=

+ beaker
-j-

Wt.

of sulphuric acid taken

Wt. Wt.
*
.
.

of test tube of test tube

beaker

+ water

+ beaker

Wt.

of water taken

From

the results calculate the specific gravity of your

sulphuric acid. no more of concentrated sul6. Heat one drop over wire gauze. dish in an acid evaporating phuric Result? c. Put into a test tube a splinter of wood and add 5 c.c.

concentrated sulphuric acid. Let stand fifteen minutes. Try the effect of a drop of concentrated sulphuric acid on paper upon cotton cloth. Wait for the result if it is
;

not immediate. Results. d. Into a small beaker put 10 grams sugar arid 5 c.c. water, and stir thoroughly. Now add 10 c.c. concentrated sulphuric acid.
Results?

Describe the product.

EXPERIMENT

XLIV.

SULPHATES.
Apparatus.
Materials.

Test tubes. Concentrated


cupric

sulphuric

acid;

solutions

of

barium

sodium sulphate; e. hydrochloric acid; liquid from Experiment XLII,


chloride,

sulphate,

dilute

68
a.

LABORATORY EXERCISES.
To
10
c.c.

water in a test tube add

1 c.c.

concen-

Result? Heat the diluted acid trated sulphuric acid. to boiling, and add 5 c.c. barium chloride solution, BaCl 2
.

Result?

The
If

precipitated substance is barium sulphate, BaS0 4 the other product is hydrochloric acid, write the
.

equation. Let the precipitate settle, pour off the supernatant liquid, and add 10 c.c. dilute hydrochloric acid to the Does the precipitate dissolve? precipitate.
b.

Repeat

a,

c.c.

of a solution of cupric sulphate,

using instead of dilute sulphuric acid 5 CuS04 Results?


.

Equation? Repeat again, using 5 c.c. of sodium sulphate solution, Na2 SO 4 with 5 c.c. barium chloride solution. Result?
,

Equation?
In general, if a solution gives with barium chloride Note. solution a white precipitate insoluble in dilute hydrochloric acid, we are reasonably sure that the unknown solution contains sulphuric acid or a sulphate.
c. Treat the liquid obtained in Experiment XLII, e, with barium chloride solution. Result? What effect

did nitric acid have


plete the equation,

upon

the sulphur dioxide?

Com-

SO2 +O+H2 O

>

CARBON.

69

EXPERIMENT XLV.
CARBON.
Apparatus.
beaker.
Materials.
lead), soft

Tongs,

test

tubes,

iron

dish

with a cover,

Charcoal (lumps and powder), graphite (pencil


coal,

hydrogen sulphide solution, litmus solution,

brown
a.

sugar, animal charcoal.

Hold a piece of charcoal in the Bunsen flame (use and describe its combustion. Repeat with graphite (pencil lead) and with soft coal. b. Fill an old test tube one-fourth full of bits of wood, and heat. Results? Bring a burning match to the
tongs)

mouth
ucts.

of the tube.

Result?

Describe the other prod-

What

is

the residue?

c. Hold a piece of wood charcoal under water in a beaker for two minutes. What appears on its surface?

Conclusion?
d.

Heat powdered wood charcoal


c.c. of it

or animal charcoal

for five minutes hi a covered iron dish.

Let

it

cool,

add 2

to 5

c.c.

hydrogen sulphide solution.

and Shake

thoroughly and filter. Compare odor of filtrate with that of the solution taken. Conclusion? e. Boil 5 c.c. litmm solution two minutes with 2 c.c. of
the freshly ignited charcoal, and filter. Result? using 5 c.c. of a solution of brown sugar with 2
charcoal.
c.c.

Repeat, fresh

Result?

70

LABORATORY EXERCISES.

EXPERIMENT

XLVI.
I.

CARBON DIOXIDE,
Apparatus.
lecting bottles.

Generating bottle, stopper with

thistle

tube and

delivery tube, pneumatic trough, beaker, test tubes,


Materials.
a.

and

col-

Marble, hydrochloric acid, litmus, lime-water.

Place in a bottle enough marble (a form of calcium

carbonate, CaCOs) to cover the bottom, add enough water to close lower end of the thistle tube, insert stopper,

and add concentrated hydrochloric acid through the thistle tube. Add more acid when it is needed. Collect
the carbon dioxide

(CO 2 ) over water, rejecting the first bottle of the gas. See, also, Experiment XX. b. Put into a bottle of the gas wet litmus paper (red
and blue) and a burning match. Results? c. Pour a bottle of the gas into a beaker
of air.

Test

the gas in the beaker with a burning match. Result? Conclusion as to the specific gravity of the gas? d. Fill a test tube with the gas by air displacement,

add

5 c.c. cold water, close tube securely with

thumb,
Result?

shake
e.

vigorously,

and

open

under

water.

Conclusion?

Let
Its
(cf.

Pass the gas into lime-water, the precipitate settle. It is


is

Ca(OH) 2
calcium

Result?
carbonate.

formation with lime-water

a test for carbon dioxide


Result?
Boil

Experiment V,

e)

Now pass a vigorous stream of the


the

gas into the tube five minutes. contents of the tube. Result?

EFFECT OF HEAT ON CARBONATES.

71

EXPERIMENT

XLVII.
II.

CARBON DIOXIDE,
Apparatus.
Materials.
a.

Beakers, delivery tube, test tubes. Lime-water, sodium bicarbonate, tartaric acid.
c.c.

Mix 2

and

tartaric acid

each of sodium bicarbonate (NaHC0 3 ) (H^C^^e) in a mortar. Is a change

Put half of the powder into a test tube, and add water. Result? Identify the gas. b. Put the remainder of the mixture from a in a test tube, add 10 c.c. water, and, as soon as you are able, imapparent?
prison the gas by holding your thumb upon the mouth of the test tube. Now Effect upon the effervescence?

remove your thumb.


c.

Effect?

Explain.
delivery tube into 5

Blow your breath through a


lime-water.

c.c.

Result?

Conclusion?

d.

Expose 5

c.c. clear

hours.
air (c/.

Result?

How

lime-water to the air for several does carbon dioxide get into the

Experiment V,

e)?

EXPERIMENT

XLVIII.

REDUCTION BY CARBON. EFFECT OF HEAT ON


CARBONATES.
Apparatus.
test tubes.

Ignition tube, delivery tube, rubber connector,

Materials.

Lead monoxide, powdered

charcoal, lime-water,

magnesite.

72
a.

LABORATORY EXERCISES.
Mix
1

PbO, with one-third its on smooth paper. Into powdered charcoal, the ignition tube put enough of the mixture to make a
c.c.

lead monoxide,

volume

of

layer 1 cm. thick, support the tube almost horizontally,

and attach a delivery tube leading into 5 c.c. lime-water. Heat the lead monoxide persistently for ten minutes, Result? What cool it, and pour it out on the table. was evolved? the Write equation. gas
6.

Fill

the ignition tube one-fifth


3,

full of

chips of mag-

nesite,

MgCO
gas
is

and

set

What
tain?

evolved?

persistently. up What, then, does the residue conit

as in a.

Heat

Write the equation.

EXPERIMENT
FLAMES.
Apparatus.
Materials.
a.

XLIX.

Bunsen burner and

tongs.

Candle, piece of porcelain, white paper.

Examine

a vertical section of

Sketch carefully the non-luminous flame. it as you see it. Make drawing 4

cm. long. b. Do the same with a luminous Bunsen flame 2 cm. high. Repeat with a candle flame. c. Press the colorless Bunsen flame for a moment

upon paper lying on your table. The paper should not burn up. Result? Hold a piece of glass tubing about 1 dm. long at an angle of forty-five degrees, with the lower end inside the central part of the non-luminous flame, and apply a lighted

BROMINE.
match

73

to the other end. Result? What do these experiments show as to the inner region of the flame? d. Hold a piece of porcelain (broken evaporating dish)

by means

What
lain

of tongs in the luminous flame. Result? substance is in excess here? Now hold the porce-

in
is

the

colorless

flame

for

some time.

Result?

What

in excess in this flame?

EXPERIMENT
BROMINE.
Apparatus.
Materials.

L.

Beaker, 100

c.c. flask,

test tubes.

Potassium bromide, powdered manganese dioxide, dilute sulphuric acid, litmus paper, calico, carbon disulphide, chlorine-water, sodium hydroxide.
Caution.
If possible,

work

in a

gas-chamber or hood.

a. Into a flask put an eighth of a test tube of potassium bromide (KBr) crystals, half as much powdered manganese dioxide, and half a test tube of dilute sulphuric acid. Support the flask over wire gauze, and attach the cork stopper and a doubly bent delivery tube

The The
b.

reaching into a test tube three-fourths full of cold water. delivery tube must be without rubber connections. test tube should rest in a beaker of water (cf. Ex-

periment XI).

Warm

tillate

the flask carefully until a dark brown dispasses over. Is it heavier or lighter than water?

Do

not inhale the vapor, and do not get liquid bromine on your hands.

74

LABORATORY EXERCISES.
over,

When no more bromine comes

remove

first

the delivery tube and then the flame. " bromine-water." solution is
the air from the bromine? Pour off possible without pouring out water to the bromine. Pour water upon litmus paper
c.

The light-brown

Wave
of

test

tube toward the nose.


as

Odor

as

much bromine-water

the bromine, and add more a few drops of the bromine-

and upon colored

calico.

Results?

water in a test tube add 1 c.c. carbon with thumb, and shake vigorously. Results? Where is the carbon disulphide? Now add Result to the J c.c. bromine- water and shake again. color of the water? To that of the carbon disulphide? This effect on the carbon disulphide is a test for free
d.

To

c.c.

disulphide, close tube

bromine.
e. To 5 c.c. of potassium bromide solution add 1 c.c. carbon disulphide and shake. Result? Now add two or three drops of chlorine-water (make as in Experiment XXI, i), close the tube, and shake it as before. Results? Action of chlorine on potassium bromide? Equation? /. To the liquid bromine saved from c add sodium hydroxide solution, a cubic centimeter at a time, shaking (Do not close the tube with the thumb!) thoroughly.

Result?
2

The equation

is,

NaOH-f 2 Br

NaBr+NaBrO+H 0.
2

sodium
hypobromite

IODINE AND HYDRIODIC ACID.

75

EXPERIMENT

LI.

IODINE AND HYDRIODIC ACID.


Test tubes, beaker, flask. Potassium iodide, manganese dioxide, sulphuric acid, iodine, carbon disulphide, chlorine- and bromine-water, starch, alcohol, hydrogen sulphide, silver nitrate solution, soApparatus.
Materials.

dium carbonate,
a.

litmus.

c.c.

Powder potassium iodide (KI), mix 1 c.c. of it with of manganese dioxide, add 2 c.c. water and then
concentrated sulphuric acid. Result? When the warm the tube gently, and then let it

1 c.c.

action slackens,
cool.

Describe what you find in the tube. It is iodine. its that of with chlorine and Compare preparation
6.

bromine.

Warm
c.c.

with 10
1

a crystal of iodine (gently, not to boiling) water for a few seconds. Does the iodine

dissolve readily?
c.c.

sult?

Cool the wa.ter and add 3 c.c. of it to carbon disulphide. Shake the closed tube. ReThis is a test for free iodine. Save the iodine

solution.
c. Shake 5 c.c. potassium iodide solution with 1 c.c. carbon disulphide. Result? Add a drop of chlorinewater and shake again. Result? What effect has chlorine upon potassium iodide? Repeat, using bromine-

water instead of chlorine-water. Write both equations. Mix 2 c.c. d. Make a starch solution as follows: and cold 5 c.c. with starch water, pour the powdered emulsion into 30 c.c. boiling water. Boil for a minute or

76

LABORATORY EXERCISES.

two, and then cool. To 3 c.c. of the solution add a drop of the iodine solution of b, shaking. Result? To 3 c.c. of the starch solution add one drop of a potassium iodide solution and then one drop of chlorineor bromine- water. Result?
e.

Heat a

crystal or

two

test tube.

Result?

Let
e

cool.

of iodine hi a dry, inclined Result? Effect of iodine

on the skin?
/.

On wood and

paper?

To

the iodine of
is

In which

add 5 c.c. ethyl alcohol, C 2 H 5 OH. iodine more soluble, water or alcohol?
is

An
20

alcoholic solution

often called a tincture.


of

powdered iodine in a flask add water and then pass in hydrogen sulphide (gaschamber!) until the iodine disappears. Results? Boil
g.

To

one-half a

c.c.

c.c.

the solution gently two minutes, and filter it. Identify the precipitate by igniting a little on a piece of porcelain, Odor? Test the nitrate with red and blue litmus,
Results?
tion.

Result?

Result?

Add a drop of it to 1 c.c. silver nitrate soluAdd some to 1 c.c. solid sodium carbonate What substances are formed from hydrogen
Equation?

sulphide and iodine?

EXPERIMENT

LIL
ACIDS.
con-

COMPARISON OF THE HALOGEN


Materials.

Potassium chloride, bromide, and iodide;

centrated sulphuric acid, litmus.

have small amounts of potassium iodide, respectively; treat each with a few drops of concentrated sulphuric acid. Rea.

Three

test tubes

chloride, bromide,

and

HYDROGEN PEROXIDE.
suits?

77

across the mouth of each tube. Test the gas of each with blue litmus. ReNote carefully the odor of each gas. What odors sult? beside that of the acid do you get in the tube of potassium

Blow your breath

Result?

iodide?
6.

Heat

this tube.

Result?

What colors the gives a colorless gas? gas in each of the two other cases? From the amount of coloration, tell which of the three halogen acids is most
Which tube
easily

decomposed

into

its

elements.

Which

least.

EXPERIMENT

LIII.

HYDROGEN PEROXIDE.
Hydrochloric acid, barium peroxide, starch sopotassium iodide solution, manganese dioxide, potassium permanganate, ether, potassium dichromate solution, splinter.
Materials.
lution,
a.

acid

To 25 c.c. water add 5 c.c. concentrated hydrochloric and then 3 grams powdered barium peroxide, Ba0 2
,

little

at a time, stirring.

Filter the solution;

it

should

contain hydrogen peroxide, 2 O2 6. To 5 c.c. starch solution add a drop of potassium iodide solution, and then a few drops of the hydrogen
.

peroxide solution. Result? c. To 3 c.c. of the solution of a add 3

c.c. ether.

Do

they mix? Is the ether above or below? Now add one and drop of potassium dichromate solution. Close tube shake gently. Result? d. To 5 c.c. of the hydrogen peroxide solution add 1 c.c. manganese dioxide. Result? Test gas with

powdered

a glowing

splinter.

Result?

78
e.

LABORATORY EXERCISES.
To
three crystals of potassium permanganate in a c.c. water and then 5 c.c. of the hydrogen

test

tube add 2

peroxide solution. Result?

Result?

Test with glowing splinter.

EXPERIMENT

LIV.

PHOSPHORUS AND PHOSPHORIC


Apparatus.
rating dish, file. Materials. Red
filter

ACID.

Test tubes, small ignition tube, tongs, evapo-

and yellow phosphorus, carbon

disulphide,

paper, phosphoric acid,

ammonium

hydroxide, powdered

disodium hydrogen phosphate; magnesium sulphate, ammonium chloride, silver nitrate, and calcium chloride solutions.
Caution.
Ordinary, yellow phosphorus must be handled never with fingers! It must be kept and cut
pieces of
it

only with tongs,

under water.

No

must get

into your locker;

and

every dish that has contained phosphorus must be heated, so that the phosphorus may be completely burned.

Do

not bring carbon disulphide near a flame!

a. Put half a c.c. of red phosphorus into a test tube, and add 3 c.c. carbon disulphide. Result? Filter, and

let

in a hood, or

the carbon disulphide evaporate, without heating, where its vapor will not get near a flame.

Result?

Was any phosphorus


c.c.

dissolved?

carbon disulphide add a piece of yellow phosShake carefully phorus not larger than a grain of wheat. a few minutes. Result? Pour the solution, every drop
3
of
it,

To

upon a

ring stand.

piece of filter paper laid flat on %a ring of the Let the carbon disulphide evaporate with-

PHOSPHORUS AND PHOSPHORIC ACID.


out heating
it.

79

Result?

Rinse the test tube before

putting it away. b. Into a small ignition tube put a layer of red phosphorus not more than 5 mm. thick, hold tube horizontal (tongs), and gently heat end containing the phosphorus.

What
tube
stick.

collects
is

on the cold part

of the tube?

When

the

cold,

make a

and break the tube.


Result?

file-mark just below the deposit, Rub the deposit with a match
Finally, heat

Conclusion?

both tubes

red hot, so as to burn up all the phosphorus. the pieces into iron or crockery jars.
c.

Throw

To

c.c.

water add

c.c.

concentrated (ortho)

phosphoric acid, neutralize in an evaporating dish (use litmus) with ammonia, and add silver nitrate solution.

Result?
.

The
4.

precipitate

is

silver orthophosphate,
if

Ag3 PO 4
is

Write the two equations


c.c.

the

first

product

(NH HPO
4) 2

Dissolve 2

in 10 c.c. water.

powdered disodium hydrogen phosphate To half of the solution add calcium


Result?

chloride solution.

The product
Equation?

is

secondary

calcium phosphate,

CaHP0

4.

d. To 5 c.c. magnesium sulphate solution add 1 c.c. ammonia-water and 1 c.c. ammonium chloride solution, and then the disodium hydrogen phosphate solution from c. Result? The product is magnesium am-

monium
(1)

phosphate,
4

NH MgP0
4
4

4.

H O.
2
2
4

(2)

Na,HP0 +NH OH Na NH 4P0 +MgS0 4


2

Na NH P0 +H 0. MgNH 4P0 4 1 +Na2S04


4

80

LABORATORY EXERCISES.

EXPERIMENT
ARSENIC.
Apparatus.
Materials.
chloric acid,

LV.

Small ignition tube, tongs, test tube, beaker.


Arsenic trioxide
(powdered),
charcoal,

hydro-

hydrogen sulphide,

ammonium

sulphide,

sodium

hydroxide solution.

Into a small ignition tube put powdered arsenic Hold the tube trioxide, As2Oa, to the depth of 5 mm.
a.

side of the flame, so as to heat only the the end containing powder. What happens? Now slip into the tube, almost to the arsenic trioxide, a piece of charcoal about 2 cm. long. Heat the charcoal red

horizontal

and at the

hot (have tube horizontal), and then incline the tube


slightly so as to heat the arsenic trioxide while keeping Effect of charcoal upon the charcoal red hot. Result?

the oxide?
tained.
6.

Equation?

How

does the oxide come into

contact with the charcoal?

Sublime

the

arsenic ob-

Heat

half

c.c.

of

arsenic

trioxide

with 8

c.c.

dilute

hydrochloric

acid

to

gentle

boiling.

Result?

Equation?

and pass
If visible

off from any undissolved material, hydrogen sulphide for a minute. Result? product is arsenic trisulphide, As 2 S 3 (its color?),

Pour

in

write equation. and add 5 c.c.

Let

settle,

pour

off

supernatant liquid,

ammonium

sulphide to residue, shaking.

Do not get ammonium sulphide (CAUTION. on your hands!) The product now formed is ammonium it is soluble. Treat solution sulpharsenite, (NH 4 ) 3 AsS 3
Result?
;

ANTIMONY.

81

with an excess of dilute hydrochloric acid in a beaker.


Result?
c. Treat half a c.c. of arsenic trioxide with sodium Warm carefully. Result? The hydroxide solution. solution contains sodium arsenite, Na 3 AsO 3 From 6
.

and

would you say arsenic

trioxide has add, or basic,

properties?

EXPERIMENT
ANTIMONY.
Apparatus.
Materials.
acids,

LVI.

Mortar and pestle, funnel, ignition tube. Antimony, concentrated nitric and hydrochloric hydrogen sulphide, ammonium sulphide, antimony triox-

ide, tartar emetic.

a.

What

is

the

color of

metallic

antimony?

Is

it

small piece, and treat part of heavy Results? it in a test tube with concentrated nitric acid.
or light?

Powder a

Treat the remainder of the powdered antimony of a c.c. concentrated hydrochloric acid and 1 c.c. concentrated nitric acid. Warm to start the action, if
6.

with 3

necessary.
SbCls.

The solution contains antimony chloride, Let action continue for ten minutes; then add
Filter,
if

15

c.c.

water.
If

necessary,
,

and pass
still

in

hydrogen
Result?

sulphide.
If

there

is

no action

dilute

more.

the product has the formula Sr^Ss, write the equation. Treat the antimony sulphide as you did arsenic
trisulphide in Experiment LV, 6. c. Dissolve half a c.c. of tartar emetic in 5
c.c.

water,

82
add a drop
sulphide.
d.

LABORATORY EXERCISES.
of hydrochloric acid, and pass in hydrogen Result? Conclusion?
in

with charcoal,

Heat antimony trioxide (Sb2 03) as you did arsenic

an ignition tube
Results?

trioxide.

EXPERIMENT
BISMUTH.
Apparatus.
Materials.
acids,
a.

LVII.

Mortar and

pestle, beaker, test tubes. nitric

Bismuth, concentrated
crystals,

and hydrochloric

bismuth nitrate

hydrogen sulphide.

What

or light?

Treat
b.

is the color of bismuth? Is the metal heavy Malleable or brittle (test with the pestle)? a bit with concentrated nitric acid. Result?

Products?

To

half a c.c. of

bismuth nitrate

crystals,

Bi(NO3 )

3,

Result? If the product water, and shake. has the formula BiONOa, write the equation. Now add nitric acid (concentrated) a drop at a time, heating to
c.c.

add 5

amount

boiling after each drop. of acid.

Result?

Use the

least possible

c. Put half of the solution from b into a beaker, and add much water. Result? Compare with first part of b. d. To the remainder of the acidified solution of bismuth nitrate from b add hydrogen sulphide. Result? The visible product is bismuth sulphide, Bi 2 S 3 Write the
.

equation.

BORAX AND BORIC

ACID.

83

EXPERIMENT

LVIII.

BORAX AND BORIC


Apparatus.
beaker.
Materials.
ide,

ACID.
glass rod, test tubes,

Platinum wire sealed into

Borax, potassium dichromate, manganese dioxhydrochloric acid, and sodium carbonate (solid).

Make a loop 2 mm. in diameter on the a. Borax Bead. end of a platinum wire sealed into a piece of glass tubing. Heat the loop to redness, and dip it into powdered borax, Na2B 4 7 10 H 2 O. Heat the adhering borax just within the outer edge of the Bunsen flame, at the place where
.

the

flame

is widest.

This

is

What happens

first?

Heat

the fusing zone of the flame. until the borax melts to a

If there is not enough borax to fill transparent glass. This glassy lump the loop, add more, and heat again. is called the borax bead.
b. Touch the hot bead to a tiny speck (less than half 2 Cr 2 O7, as large as a pin's head) of potassium dichromate, and heat at the top of the flame until the dichromate is Remove the Color? absorbed by the bead.

completely
the wire.
c.

bead by plunging

it

while hot into water,

and wie

it

off

Make
i.

new

ganese dioxide.
burner, Color?
e.,

Heat
just

of manbead, and touch it to a speck first in the oxidizing flame of the above the visible tip of the flame.
e.,

it in the reducing region, i. cone. the of bright blue interior above the tip five examining for minutes, there persistently

Now

heat

just

Heat it it from

84
time to time.
flame.
d.

LABORATORY EXERCISES.
Result?

Heat

it

again in the oxidizing

Result?
Dissolve 5

Boric Acid.

grams powdered

borax

in 10 c.c. hot water, and add 10 c.c. concentrated hydrochloric acid. Set aside until next laboratory period. Filter off Result? The product is boric add, 3 3

H B0

the crystals, wash them on the


water, and dry them on
e.

filter

with a

little

cold

add

fresh filter paper. Dissolve the crystals of boric acid in hot water, and Result? the solution to a lump of sodium carbonate.

EXPERIMENT

LIX.

SODIUM COMPOUNDS.
Test tubes, stopper and delivery tube, magniApparatus. fying glass, platinum wire, watch glass or glass slip. Materials. Sodium bicarbonate, lime-water, sodium carbonate
ride,
(solid

and

in solution),

barium

chloride,

sodium chloride, calcium chlosodium nitrate and sulphate, hydrochloric

acid.

a.

sodium* and
6.

Experiment XII for the properties of action on water. Heat 2 c.c. powdered sodium bicarbonate carefully
Refer to
its

in a test tube having a delivery tube that passes into lime-water. Result? Is there any other volatile prod-

uct?

When no more

test tube), let the

gas is evolved (do not melt the product in the tube cool, and then add

2 c.c. cold water. Note the temperature effect. Compare with this the action of anhydrous sodium carbonate

POTASSIUM COMPOUNDS.

85

upon water. What are the products formed by heating sodium bicarbonate? Equation? c. Heat 2 c.c. sodium chloride with 5 c.c. water in a test tube; filter; and let some of the filtrate evaporate completely on a glass slip or a watch glass. Examine
the crystals with a magnifying glass,
if

possible.

Their

shape? d. Dissolve a small piece of calcium chloride, CaCl 2 in 5 c.c. water, and add sodium carbonate solution. Result? Repeat, using barium chloride instead of calcium chloride. Result? Write the equations. e. Dip a platinum wire with a glass holder (c/. Experi,

ment LVIII, a) into 5 c.c. concentrated hydrochloric acid in a test tube, and then heat the wire in the Bunsen flame until the flame remains colorless. If necessary, dip the wire more than once. Now wet the clean wire
with the acid, dip it into powdered sodium chloride, and heat it. Effect on the flame? nitrate /. Clean the wire and repeat e, using sodium sodium with instead of sodium chloride. Repeat again
sulphate.

What

color

do sodium

salts give to the flame?

EXPERIMENT

LX.

POTASSIUM COMPOUNDS.
Watch glass, iron dish, test tubes, beaker or Apparatus. evaporating dish, platinum wire, copper wire. Potassium chloride, sodium nitrate, sulphur, Materials.
barium chloride
water,
solution, potassium

hydrogen

tartrate, lime-

dilute sulphuric acid,


nitrate,

concentrated hydrochloric acid,

potassium

and potassium sulphate.

86
a.

LABORATORY EXERCISES.

Heat 8 grams of potassium chloride and 10 grams sodium nitrate with 20 grams of water until there is complete solution, and boil off half of the water over the wire gauze? Result? Let the precipitate settle and
of

pour the solution into a test tube. Wash the residue with 5 c.c. cold water, and then dissolve it in the smallest Pour a few drops of the possible amount of hot water. Result? Comsolution in a watch glass and set aside. in the with those obtained crystals pare Experiment LIX,
c.

Conclusion?

What happens
solution?

in the test tube containing the original


visible

The
3
c.c.

product

is

potassium

nitrate,

KN0
6.

Mix

piece of paper with 1 c.c.

Result? Let the product cool, boil with 10 c.c. water in a test tube, and add to 5 c.c. Result? See Experiment of it barium chloride solution. 6. the What is XLIV, product of the deflagration of
it

the mixture, at no wire gauze).

powdered potassium nitrate on a clean powdered sulphur, and pour arm's length, upon a hot iron dish (use

potassium nitrate and sulphur?


c.

Heat an iron dish red


Results?

hot,

and pour upon

it
6

c.c.

powdered potassium hydrogen


of tartar).

tartrate,

KHC H O
4

(cream

Color of residue?

minutes longer at red heat, a glass rod occasionally. When the dish

Heat it five the down with mass pressing


is

cool, treat

the residue in a test tube with dilute sulphuric acid. After all evolution of gas ceases, identify the gas by
placing in the

mouth of the tube a looped copper wire a holding drop of lime-water. What remains undissolved? What substance would you find in plant ashes if the plants contained potassium salts of organic acids?

DISTINCTIONS BETWEEN METALS.


d.

87

dip

Clean a platinum wire as in Experiment LIX, e; into strong hydrochloric acid, and then into powdered potassium chloride, and heat it in the flame.
it

Result?
chloride.

Repeat, using potassium nitrate instead of the Use the sulphate. Results? What color do

potassium compounds give to the flame?

EXPERIMENT

LXI.

AMMONIUM AMALGAM.
Materials.

DISTINCTIONS BETWEEN
sodium amalgam, sodium two unknown substances.
c.c.

THE ALKALI METALS.


Ammonium
chloride,

and potassium
a.

chlorides, tartaric acid,


c.c.

Dissolve 2

ammonium

chloride in 5

water,

sodium amalgam (Na+Hg). Results? The product is ammonium amalgam. Note what happens Odor? Reaction of solution? to it.

and add a piece

of

Note.

Do

not throw away the resulting mercury, but ask


it.

what to do with
6.

Add

c.c.

water to 3
c.c.

c.c.

chloride

and shake thoroughly.


it

powdered potassium Pour off the solution

and add to
acid,
2

of a concentrated solution of tartaric


this

H C4H

4 O6.

Make

tartaric acid with 15 c.c.

water.

by shaking 5 c.c. powdered Wait for result. Result?

The product

potassium hydrogen tartrate. Equation? in place of potasc. Repeat 6, using sodium chloride Result? Repeat again, using ammosium chloride. Result? in nium chloride place of potassium chloride.
is

88

LABORATORY EXERCISES.

d. From Experiment XXXIII, b and c, tell what happens when ammonium salts are treated with alkalies. How distinguish between sodium salts on the one hand and ammonium and potassium salts on the other? Between sodium salts and potassium salts (two ways)? e. Get from the instructor two unknown substances, and determine if they are salts of sodium, potassium, or

ammonium.

EXPERIMENT
CALCIUM.

LXII.

Apparatus. Triangle of iron wire, ring stand, blast-lamp, evaporating dish, platinum wire, arid coin. Materials. Lumps of marble, lime-water, red litmus paper,
old mortar, plaster of Paris, paper, calcium chloride, calcium
sulphate,
a.

and ammonium carbonate

solution.

Touch a
in

piece of wet red litmus paper with a piece

of marble.

marble about upon a ring of the ring stand, and heat the marble ten to fifteen minutes in the hottest Bunsen flame in a blastlamp, if possible. When the marble is cold, touch wet, red litmus with the part that was heated. Result?
of

Result?

Support a lump

c.c.

volume on a

triangle of iron wire laid

Explain.

What

products are formed

when marble

is

Experiment XL VIII, 6)? Slake about 5 c.c. of quicklime by adding to it water, drop by drop, as long as the water is taken up readily. Wait for the result, and describe it. Is there a temperaheated
(c/.

ture effect?

Equation?

STRONTIUM AND BARIUM.


b.

89

a piece of old mortar in a test tube add dilute hydrochloric acid. Identify the gas. What does fresh mortar absorb from the air?
c. Stir 10 c.c. plaster of Paris in an evaporating dish with enough water to form a fairly thick paste. Put the paste upon a piece of paper, and push into it a coin slightly coated with vaseline. At once wash the evaporatLet the paste and coin stand an hour or more. ing dish.

To

Carefully remove the coin from the plaster. d. To a solution containing a calcium

Result?
salt,
i. e.,

calcium ions, add ammonium carbonate solution. sult? See Experiment LIX, d.
e.

Re-

Clean a platinum wire as in Experiment LIX,

e,

and determine what


flame.

color calcium chloride gives to the


sulphate.

Repeat with calcium

Be

sure to have

concentrated hydrochloric acid upon the wire.

EXPERIMENT

LXIII.

STRONTIUM AND BARIUM.


Apparatus.
Materials.

and

nitrate;

Platinum wire and test tubes. Strontium chloride and nitrate, barium chloride solutions of strontium and barium chlorides;

ammonium
a.

carbonate solution; dilute sulphuric acid.

Treat 2
of

drops

strontium chloride solution with a few Result? ammonium carbonate solution.


c.c.

Repeat,
chloride.
b.

using barium chloride in place

of

strontium

Write equations. Treat 2 c.c. strontium chloride solution with dilute

90
sulphuric

LABORATORY EXERCISES.
acid.

Result?

See

Experiment

XLIV,

a.

Equation? c. Clean the platinum wire as in Experiment LIX, e, and heat a bit of strontium chloride in the flame. Repeat with strontium nitrate, Sr(NO 3 )2. Results? d. Repeat c, using the corresponding barium salts. Results? How distinguish between calcium, strontium, and barium salts?

EXPERIMENT

LXIV.

MAGNESIUM.
Apparatus.
Materials.
tions of

Tongs, test tubes.

Magnesium wire, dilute hydrochloric acid, solumagnesium sulphate and chloride, disodium hydrogen phosphate, and ammonium chloride and hydroxide, magnesite.
a. Hold a piece of magnesium wire 2 cm. long in the Result? Describe the product. flame (use tongs). b. Treat a second piece of magnesium with dilute Result? Identify the gas, and write hydrochloric acid.

the equation. See Experiment X. c. To 2 c.c. of magnesium sulphate solution add sodium carbonate solution. Result? Repeat, using mag-

nesium chloride instead of the sulphate. d. See Experiment LIV, d, for the action of a solution a containing magnesium salt with disodium hydrogen phosphate and ammonium hydroxide. Rewrite the
equations here. Repeat that

experiment

with

magnesium

chloride

solution instead of the sulphate.

Equation?

ZINC.
e.

91

Treat a small piece (half a c.c.) of magnesite with nitric acid. Result? Identify the gas, and write the equation.
dilute

From Experiment
upon magnesite.

XL VIII,

6,

tell

the effect of heat

EXPERIMENT LXV.
ZINC.
File or sand-paper, knife, iron dish with Apparatus. bottom, test tubes, mouth blowpipe.
flat

and copper; zinc dust; solutions sodium hydroxide, and ammonium sulphide; dilute sulphuric and hydrochloric acids; hydrogen sulphide;
Materials.
Zinc, tin, lead,
of zinc sulphate,

stick of charcoal.

with a file or with or hard soft (use a knife sand-paper. or rough edge of glass) ? Place a burner below the center At equal distances from the center of an iron dish. of zinc, tin, lead, and copper, and determine place pieces the order in which they melt. Return the metals to the
a.

Clean part of a piece


Color?

of zinc

Is zinc

proper bottles. b. Heat a piece of zinc on charcoal with the oxidizing flame and with the reducing flame produced by the mouth
blowpipe.
Results?

To do

this proceed as follows:

Hollow out a depression near one end of the charcoal, and To make the blowpipe flame, have a it put the zinc. luminous Bunsen flame 4 cm. high, and hold the blowpipe so that the flame produced will be inclined about 30 degrees to
into

the horizontal plane.

92
To make an

LABORATORY EXERCISES.

oxidizing flame, hold the end of the blowpipe luminous flame, a centimeter above the tip of the dark, inner cone. Hold the charcoal at such a distance that the zinc is in the outer, faintly-luminous part of the blowpipe
inside the

flame.

To make a reducing flame, hold the tip of the blowpipe just at the outer edge of the flame at its middle part, and hold the assay (here, zinc) much nearer the blowpipe than in the oxiThe proper region is just at the tip of the inner, of cone the blowpipe flame. light-blw
dizing flame.

has hydrochloric acid -upon zinc? See Experiment VIII for the action of dilute sulphuric acid, and Experiment XVII for the behavior
c.

What

action

Equation?

with 5 c.c. sodium hydroxide Test evolved gas with a solution, and heat carefully. flame. Result? The solution contains sodium zincate, Na2 Zn02 Write the equation. e. To 2 c.c. zinc sulphate solution add a drop of sodium
.

of zinc sulphate crystals, d. Mix 1 c.c. zinc dust

ZnSO 4

H O,
2

when

heated.

hydroxide solution.
precipitate? tube.

Result?

What, probably,

is

the

Equation? Repeat with a second test Now add to the first tube dilute hydrochloric acid, shaking. To the second tube add an excess of sodium
Results? The alkaline hydroxide, shaking. contains sodium zincate. Equations?
solution

What do

these experiments

show as to the nature

of

zinc hydroxide?
/. To 10 c.c. zinc sulphate solution add a drop of dilute Result? sulphuric acid, and then hydrogen sulphide. Put the solution into a beaker and add 5 c.c. ammonium

sulphide solution, zinc sulphide, ZnS.

stirring.

Result?

The product

is

Color?

Equation?

EQUIVALENT OF

ZINC.

93

Add
water,

10

c.c.

then pour
This
is

off

water, stir the mixture, let it settle, and the supernatant liquid. Add 15 c.c. more
"

and decant, i. e., pour off the water. washing by decantation." To the zinc sulphide add dilute sulphuric acid. Result?
stir, let settle,

called

What

is

the

gas?

sulphide precipitated

Equation? Why was not by hydrogen sulphide?

zinc

EXPERIMENT

LXVI.

EQUIVALENT OF ZINC.
Apparatus.
Materials.

Same

Zinc, in sheet

as in Experiment X. form or in sticks; dilute

(5%)

sul-

phuric acid.
a.

did

Dissolve zinc in dilute sulphuric acid just as you magnesium in Experiment X, and find the volume

of hydrogen liberated by a known weight of zinc. Use from 0.45 gram to 0.55 gram of zinc. If the zinc is in

but a little impurity, If the zinc is remain insoluble. chiefly carbon, therefore wind about with react it will difficulty; pure, the zinc a piece of platinum wire or a narrow strip of
sheet form,
it

will react readily;


will

Set the apparatus aside until the zinc then proceed as in Experiment X. b. Reduce the volume of hydrogen to standard conditions, and calculate the weight of the hydrogen obtained. Finally, solve for x in the proportion,

platinum

foil.

is

in solution;

Wt.

of zinc taken

Wt.

of

hydrogen obtained

::

x: 1.

The value

of

will

be the equivalent of zinc.

94

LABORATORY EXERCISES.

EXPERIMENT
Cadmium

LXVII.

CADMIUM.
Materials.

sulphate,

hydrogen

sulphide,

am-

monium
a.

sulphide.

Dissolve completely not more than 1 c.c. cadmium CdS0 4 in 5 c.c. water, and add hydrogen sulphide in excess. Result? The visible product is cadsulphate,

mium

Equation? What other have you had? Wash the precipitate by decantation, and treat it with 5 c.c. ammonium sulphide. Result? How distinguish between cadmium sulphide and other sulphides of the same color?
sulphide,

CdS.

Color?

sulphides of the

same

color

EXPERIMENT

LXVIII.

MERCURY.
Apparatus.
Materials.

Pipette (medicine dropper).

phide, iodide solutions,

Mercury, concentrated nitric acid, hydrogen sulhydrochloric acid, sodium hydroxide and potassium

ammonium

hydroxide, zinc, and copper.

Caution.

Do not throw mercury away;

Before working with mercury remove all rings. but ask what you are to do with it.

a. By means of a pipette take from the mercury bottle a globule three times as large as an ordinary water drop; add to it 2 c.c. water and 2 c.c. concentrated

MERCURY.
nitric

95
until

acid.

this

may

Result? Let take some hours.

stand

action

stops;

b. While waiting for a, dissolve a globule of mercury the size of a water drop in concentrated nitric acid;

this

gives

mercuric

nitrate,

Hg(NO

3) 2.

Equation
c.c.

(cf.

Experiment
c.

XXXVII,

0)?

Dilute with 15
(b)
is

water.

To

c.c.

mercuric nitrate solution

add hydrogen
mercuric
sul-

sulphide.
phide,
d.

Result?

The

precipitate

HgS.

Equation?
solution,

Add

to separate portions of the nitrate solution,

hydrochloric acid, sodium hydroxide potassium iodide solution, respectively.

and

Results?

Add

the

potassium iodide drop by drop, noting changes. Write equations where possible.
Note.

With sodium hydroxide we should expect mercuric

hydroxide, and water.


e.

Hg(OH)

this,

however, decomposes into the oxide

Note the

result of a.
3
;

The

crystals are mercurous

nitrate,

pour out into a beaker, and add 15 c.c. water and a drop of strong nitric acid. nitrate solution of e /. To 2 c.c. of the mercurous

HgN0

hydrogen sulphide. The precipitate is mercuric Write the equation. sulphide and mercury. mercurous instead of the mercuric g. Repeat d with the

add

nitrate.

tate

With sodium hydroxide the precipiResults? mercurous oxide, Hg2 O. Write the equations. Treat the precipitate produced by hydrochloric acid with ammonium hydroxide. Result?
is

Into the rest of the mercurous nitrate put a strip Results? Now rub them of zinc and a copper wire.
h.

dry.

Results?

96
i.

LABORATORY EXERCISES.
Classify the results of
c,

d, f,

and

g in five vertical

columns.

Formula

of

Precipitant.

SILVER.

97
1

Result? Repeat, having the cupric sulphate hot, and then add the sodium hydroxide. Result? The last How formed (cf. precipitate is cupric oxide, CuO. Experiment LXVIII, d and 0)?
d. From Experiment XLI, b and c, tell the effect of hydrogen sulphide upon cupric sulphate. Equation? Pass hydrogen sulphide into cupric nitrate solution. Result? Equation? What is the effect of heating blue vitriol (cf. Experiment XVII, d)? 6. Dissolve half a c.c. powdered grape-sugar, C 6 Hi 2 6 in 2 c.c. water, and add it to 5 c.c. cupric sulphate solution. Now add sodium hydroxide solution, shaking Color? until the precipitate first formed is redissolved.
,

Warm
effect
/.

Let stand. Results? carefully, noting changes. is It Color of product? cuprous oxide, CuzO. What

had the grape-sugar? Put an iron nail into cupric sulphate

solution.

Result?

EXPERIMENT LXX.
SILVER.
Materials.
Silver
foil,

silver nitrate solution, nitric acid, so-

and potassium thiosulphate; solutions of sodium chloride filter sulphide. and hydrogen paper; cyanide; bromide, iodide,

dium

In a test tube treat a piece of silver foil with 2 c.c. concentrated nitric acid. Result? Equation? Dilute
a.

with water to 10
6.

c.c.

To

c.c.

of the solution of a

add 5
(cf.

c.c.

sodium

chloride solution.

Result?

Equation

Experiment

98
XXII,
j)?

LABORATORY EXERCISES.
Boil

the

contents
filter

of

the

tube.

Result?
it

Get the precipitate on


sunlight.
c.

paper, and expose

to

Result?
5
c.c.

add 1 c.c. potassium bromide Heat to solution. boiling, pour off the superto half of the precipitate sodium add and natant liquid, O thiosulphate solution, Na2S 2 3 (make this by dissolving Result? Expose the other half the crystals in water). on filter paper to sunlight. Result? d. To 1 c.c. silver nitrate solution add 1 c.c. potassium
of solution a

To

Result?

iodide solution.
e.

Result?
silver

Equation?
solution

To

c.c.

nitrate

add hydrogen

sulphide.

Result?
1
c.c.

Equation?
nitrate

/.To
cyanide

silver

solution

add potassium
Equation?

solution,
it,

drop by drop.

Result.

Continue adding

The
i. e.,

shaking, until it is in excess. Result? solution contains the double cyanide, KCN.AgCN, KAg(CN) 2 Add sodium chloride solution. Result?
.

Explain the result in terms of the ionic theory

(c/.

Experiment

XXX).

EXPERIMENT LXXI.
ALUMINUM.
Apparatus.
Materials.

Aluminum

Test tubes, tongs, blast-lamp. wire and filings, white muslin, hy-

drochloric acid;

phate,

solutions of sodium hydroxide, aluminum sulsodium carbonate, alum, ammonium hydroxide, and cochineal; powdered alum, sodium bicarbonate, potassium

sulphate,

ammonium

sulphate,

aluminum

sulphate.

ALUMINUM.

99

a. Determine whether aluminum is a conductor of heat as in Experiment LXIX, a. Does the wire melt in the Bunsen flame (use tongs)? Try the blast-lamp. Result?
6.

To 2

c.c.

aluminum

filings

add 5

c.c.

hydrochloric acid, and warm.

Result?

concentrated Test the gas.

Equation?
the filings remaining from 6, by decantation, concentrated sodium hydroxide solution, and warm carefully. Determine the nature of the gas The solution contains sodium alumievolved. Result?
c.

Wash
c.c.

add 5

nate,
d.

Na AlO
3

(c/.

Experiment LXV,

d).

Equation?

To

c.c. of

aluminum

sulphate solution, A1 2 (SO 4 ) 3 ,

sodium hydroxide solution. Result? EquaGet half of the precipitate into a second test tube, and add an excess of sodium hydroxide solution. Result? If the solution now contains sodium aluminate,
1 c.c.

add

tion?

Na3 AlO3

write the equation.

To
acid.

the other half of the


Result?

precipitate

add hydrochloric

Equation?

Compare with
e.

this the behavior of zinc hydroxide. Dissolve as much ammonium sulphate as possible

in 5 c.c. hot water,

similarly

saturated

and add to it in a beaker 5 c.c. water with aluminum sulphate. Cool

the

mixture.

Result?

The

product

is

ammonium

Heat again to complete solution, and let stand over night. Result? Shape of crystals? /. Repeat e, using potassium sulphate instead of amalum.

monium g. To
ing
gas.
.

Results? Compare the crystals. sulphate. 5 c.c. of the solution of any aluminum salt

add

sodium carbonate solution.

Result?

Identify the escap-

A1(OH) 3

The Mix a

precipitate

aluminum hydroxide, is cubic centimeter of powdered alum

100

LABORATORY EXERCISES.

add water.

with a cubic centimeter of sodium bicarbonate, and Result? h. To 1 c.c. of a solution of cochineal add 5 c.c. alum solution, immerse a piece of white muslin, and then add

ammonium

hydroxide solution, shaking.

Results?

EXPERIMENT
IRON.

LXXII.

Test tubes, tongs, blast-lamp, magnet, beaker. filings, copper wire hydrochloric, sulphuric, and nitric acids; solutions of potassium ferrocyApparatus.
Materials.

Iron wire and

anide, ferricyanide,

and sulphocyanate;
sulphide,

ammonia

water, hy-

drogen sulphide,

ammonium

solid ferrous sulphate,

and
a.

ferric cliloride.

Compare the heat conductivity


of

of iron wire with

that

copper. fusibility in the Results?


6.

Test

its

magnetic
flame

properties;

its

Bunsen

and the blast-lamp.


c.c.

Treat 3

c.c.

iron filings in a beaker with 20

hydrochloric acid, stirring. Identify the gas. If the solution contains ferrous chloride, FeCl 2 write the equation. When action almost ceases, filter
,

dilute

Results?

c.c. of the solution. Color of filtrate? Divide the filtrate of b into four parts. To the first add a few drops of potassium ferricyanide solution, " To Turnbull's blue." Result? This is 3 Fe(CN) 6 the second portion add ammonia-water. Result. Equa-

off

10

c.

tion?
third

Note any change on standing in the air. To the part add potassium ferrocyanide, KiFe(CN)6.

IRON.
Result?

101
potassium sulpho-

To

the

last

cyanate solution,

KSCN.

portion add Result?

test tubes and beakers at once. remainder of the ferrous chloride solution of 6, and add 2 c.c. concentrated nitric acid. Heat carefully for two minutes in a beaker. Resulting

Wash

out your

d.

Filter the

color? The solution contains ferric To a drop of it in a test tube add

chloride

and

nitrate.

ferricyanide solution;

if it still

a drop of potassium gives a blue precipitate,

add 2

c.c.

more

nitric acid,

and

boil again.

Treat the resulting substance in four test tubes with the reagents used in c. Result in each case?

The

precipitate

from potassium ferrocyanide and a

ferric salt is

" Prussian blue."

e. Classify the results of c vertical columns.

and d

(last part)

in five

Formula
of

Reagent.

102

LABORATORY EXERCISES.

the other half of the ferrous sulphate solution add drops of dilute sulphuric acid, and pass in hydrogen Compare with the result without the acid. sulphide.
five

To

Now
g.

add ammonium
Dissolve

sulphide.

Result?

Equation?

FeCla, in 10 c.c. water, and pass in hydrogen sulphide at least two minutes. Result? Boil the contents of the tube, and then filter.
1 c.c. ferric chloride,

Test the
solution.

with a drop of potassium ferricyanide Result and conclusion? Determine the nature of the residue on the filter
filtrate

paper by collecting it on a piece of porcelain and igniting it. Odor? Write the equation for the action of hydrogen sulphide on ferric chloride.

EXPERIMENT

LXXIII.

NICKEL AND COBALT.


Apparatus.
Materials.
of

Platinum
borax,

wire, test tubes.


solutions

Nickel and cobalt and their nitrates;

the nitrates;

sodium hydroxide

solution,

concen-

trated, chemically pure hydrochloric acid.


a. Give the physical properties from an examination of the metals.
b.

of cobalt

and

nickel

Effect of a

To

c.c.

nickel nitrate solution, Ni(NOa)2,

magnet? add a

drop of hydrochloric acid and then hydrogen sulphide.


Result?
tion?

Now add ammonium


/.

sulphide.

Result?

Equa-

Explain the results from Experiments

XLI and

LXXII,

MANGANESE COMPOUNDS.
c.

103

6,

Make a borax bead as in Experiment LVIII, a and and determine the color given to it by nickel nitrate. d. Repeat b and c with cobalt nitrate, Co(NO 3 2 )
,

instead of nickel nitrate. Results?


e.

To

c.c.

cobalt nitrate solution add sodium hyit is

droxide solution, a drop at a time, until Results?


/.

in excess.

To

c.c.

cobalt nitrate solution

add 5

c.c.

concenResult?

trated,

chemically pure hydrochloric Dilute with water. Result?

acid.

EXPERIMENT LXXIV.
MANGANESE COMPOUNDS.
Apparatus.
Materials.

Platinum

wire, test tubes.

sulphate, potassium permanganate, ferrous sulphate, grape-sugar, ammonia-water, hydrogen sul-

Manganese

phide,
a.

and ammonium
Dissolve
4,

sulphide.

c.c.

powdered

MnS0
dilute

in 5 c.c. water.

To

half of

manganese sulphate, it add a drop of

sulphuric

Result?

Now

acid and then hydrogen sulphide. add ammonium sulphide. Result? Color?

Equation?
b.

To

Explain the results. the other half of solution a add ammonia-

water.

Result? 2
c.c.

Equation?
(cf.

potassium permanganate solution. Result? Continue, drop by drop, until the solution is Now add ammonia-water. State just faintly pink.
/)

To LXXII,
c.

ferrous sulphate solution

Experiment

add

and explain the

result (cf.

Experiment XLII,

/).

104
d.

LABORATORY EXERCISES.
Dissolve
4,

crystal

of

potassium

permanganate,

and add grape-sugar solution. Result? Explain (cf. Experiment LXIX, e). e. From Experiment XXI tell the action of manganese dioxide with hydrochloric acid; from Experiment V, with potassium chlorate; from Experiment LIU, with hydrogen peroxide; and from Experiment LVIII, a, tell the color of the manganese bead.
in water,

KMn0

EXPERIMENT LXXV.
CHROMIUM COMPOUNDS.
Apparatus.
dish, test tubes.

Chlorine generator, platinum wire, evaporating

Materials.

mate, of

Solutions of potassium chromate and dichrochromic chloride, of potassium and sodium hydroxides;
acid,

hydrochloric

alcohol, borax,

barium chloride

solution,

chrome-alum.
a.

What

is

the color of solutions of potassium di-

chr ornate (K^C^O?), potassium chromate chromic chloride (CrCl 3 )?

(K^CrOJ, and

of

b. Treat 1 c.c. of potassium dichr ornate solution with a drop of potassium hydroxide solution. Result? From the color tell what is formed.

Complete the equation,

K Cr
2

+2 KOH

+?

c. To 1 c.c. potassium chromate solution add a drop of What is Result? concentrated hydrochloric acid.

formed?
2

K Cr0 +2 HC1
2

+?+?

CHROMIUM COMPOUNDS.

105

How

can a dichromate be changed to a chromate? chromate to a dichromate?


d.

potassium chromate solution add barium Result? Equation? Repeat with chromic chloride instead of the chromate. Result? e. To 1 c.c. chromic chloride solution add a drop of
c.c.

To

chloride solution.

sodium hydroxide solution. Result? Equation? Now add the alkali in excess, shaking. Result? The solution
contains

chromite,

NaCrO2

What

other

elements

behave in this way? See Experiments LXV and LXXI. Save for g. e with potassium chromate instead of f. Repeat chromic chloride. Result? In what three ways can a chromic salt be distinguished from a chromate? g. To the clear solution of e add chlorine gas until there is no further Do this in a gas-chamber. change. Results? Test the resulting solution as in b, c, and d. Results? How can a chromic salt be changed into a chromate? h. To 10 c.c. potassium dichromate solution in an evaporating dish add 2 c.c. concentrated hydrochloric
acid

and 2

c.c.

ethyl alcohol.

Boil until bright green,

but not to dryness.


chloride solution.
solution.

Test a part of the liquid with barium Result? With potassium hydroxide

What

does the green solution contain?

How
also,

can a chromate be changed to a chromic salt? See, Experiment XLII, /. i. Refer to Experiment LVIII for the borax bead Repeat with a tiny piece of chrome-alum. Result?

test.

106

LABORATORY EXERCISES.

EXPERIMENT LXXVI.
LEAD.
Apparatus.
Materials.
File or knife, test tubes,

mouth blowpipe.

lead nitrate, droxide, lead oxide, stick of charcoal.


a.

Lead; hydrochloric, nitric, and sulphuric acids; solutions of potassium chromate and sodium hy-

File or cut off the coating

on

lead.

Is

it

soft?
sult?

Color?

Try

to

mark on paper with

lead.

hard or Re-

Refer to Experiment LXV, a, for its fusibility. Treat a small piece with hydrochloric acid, both the Results? Wash the lead, and dilute and the strong.

add 2 c.c. concentrated nitric acid and 2 c.c. water. Heat gently. Result? Write the equation (cf. Experiment XXXVII). b. Heat one-fourth of a c.c. of lead monoxide on charcoal
in

the

reducing
b.

flame
Result?

(mouth blowpipe).

See

Experiment LXV,
uct?
c.

How
lead

identify the prod-

Dissolve 2
c.c.

c.c.

powdered
Cool,

nitrate,

Pb(N0
c.c.

3) 2 ,

in 15

water, heating.
c.c.

and add to 2

of the

solution 5
tion?

Wash
c.c.

with 10
d.

dilute hydrochloric acid. Result? Equathe precipitate by decantation, and heat it water. Result? Cool the solution. Result?
of the lead nitrate solution

To

c.c.

sulphuric acid.
tion instead of

add dilute Use potassium chromate soluResult? Equation in sulphuric acid.


Result?
}

each case?

From Experiment XLI, d

tell effect of

hydrogen sul-

TIN.
phide

107

For the reduction of lead Experiment XL VIII, a. e. To 2 c.c. lead nitrate solution add a drop of sodium Result? Equation? Now add an hydroxide solution.
nitrate.

oxide

upon lead by charcoal,

see

three other hydroxides See Experiment LXXV, e. f. Put into the remainder of the lead nitrate solution a Leave it at least ten minutes. Result? strip of zinc.

Result? excess, shaking. behave in the same way?

What

Equation

(cf.

Experiment LXIX,/)?

EXPERIMENT
TIN.
Apparatus.
blowpipe.
Materials.

LXXVII.

Test tubes, stopper and delivery tube, mouth

Tin (granular and


nitric

in a bar) of

concentrated hy-

drochloric

and

acids;

solutions

mercuric

chloride,

stannic chloride, and sodium hydroxide;

ammonium

sulphide,

hydrogen sulphide,
a.

zinc, sulphur, stick of charcoal.


c.c. of

Treat about 2

small bits of tin with 10

c.c.

concentrated hydrochloric acid in a test tube. Warm gently to start the action, and when the effervescence is
vigorous attach a stopper and delivery tube and collect Result? The the gas over water. Identify the gas. solution contains stannous chloride, SnCl 2 Equation?
.

Let the action continue at least ten minutes.


b.

From Experiment LXV,


and bend
it.

of tin with that of lead, etc.


ear,

a, compare the fusibility Hold a bar of tin near your

Result?

What

color has bright tin?

Is

it

hard or soft?

108
c.

LABORATORY EXERCISES.
To
of
all
1 c.c.

c.c.

mercuric chloride solution, HgCl2 add 4 or your stannous chloride solution, and then heat.
,

Note
d.

the changes.

The

solution contains stannic

chloride,

SnCl 4
2
c.c.

To

Equation? stannous chloride solution add 5


Result?

c.c.

water

EquaWash the precipitate by decantation, and add tion? 5 c.c. ammonium sulphide (use an evaporating dish Warm gently, or beaker) and a small lump of sulphur. and stir. Result? Cool, and add dilute hydrochloric
acid in excess.

and then hydrogen sulphide.

Color?

Result?

Compare the

color with that of

the original precipitate. 2 c.c. stannous chloride solution add e. To

c.c.

concentrated nitric acid, and heat gently. The solution contains stannic chloride. Dilute with 5 c.c. water, and Color? Stannic Result? pass in hydrogen sulphide.
sulphide

SnS 2 Equation? Wash the precipitate by add ammonium sulphide and a bit of Result? Add an excess of sulphur, and warm gently. Result? dilute hydrochloric acid. Compare with the color of the original precipitate, and with that obtained at the end of d. Conclusion? stannic chloride solution add sodium /. To 2 c.c. Add an Result? hydroxide solution, drop by drop. excess. Result? What other hydroxides have behaved in the same way? See Experiment LXXVI, e. g. Pour the solution of a from any unused tin, and
is
.

decantation,

put into it a strip of zinc. Result? Equation? Compare with Experiment LXXVI, /. h. Heat a piece of tin on charcoal in the oxidizing

flame

(mouth

blowpipe).

See

Experiment

LXV,

6.

Results?

COMPOSITION OF CARBON COMPOUNDS.

109

EXPERIMENT

LXXVIII.

COMPOSITION OF CARBON COMPOUNDS.


Iron dish (sand bath), test tubes, stopper and Apparatus. delivery tube, ignition tube, rubber connector. Materials. Sugar, starch, oxalic acid, benzoic acid, pow-

dered cupric oxide, lime-water, gelatine (powdered), soda-lime,


urea, litmus.
a. In an iron dish (sand bath) heat one cubic centimeter of sugar as long as a change occurs. Repeat with Results? What starch; with a crystal of oxalic acid. proof have you that the sugar and starch contain carbon?

The
b.

oxalic acid?

Heat half a c.c. of oxalic acid crystals in a test tube. Determine whether carbon dioxide is evolved or not. Results? Heat half a c.c. of benzoic acid in a test tube.
Result?
Recall
Is there

any evidence of carbon dioxide? Experiment XLVIII, a. Repeat it, using

one-fourth of a

c.c. of benzoic acid and five times its volume of powdered cupric oxide instead of the charcoal and lead oxide. Results? Is there any evidence that hydrogen was present in the benzoic acid? What pre-

caution

is

necessary to be certain,

if it is

known

that the

cupric oxide used is slightly hygroscopic? c. Recall Experiment XXXIII, a. Repeat

it,

using

powdered

gelatine in place of the glue,

soda-lime instead of slaked lime.

and powdered Results? Repeat it

again with urea in place of the gelatine. Conclusions? If glue and gelatine represent the class of albumins, what

element must the members of this

class contain?

HO

LABORATORY EXERCISES.

EXPERIMENT LXXIX.
HYDROCARBONS.
Mortar and pestle, ignition tube 15 cm. long, Apparatus. ring stand, clamp, delivery tube, rubber connector, test tubes,
100
c.c. flask,

wire gauze, one-hole stopper, pneumatic trough,

evaporating dish.
Materials. Dry soda-lime and fused sodium acetate, lime" 95 per water, bromine water, concentrated sulphuric acid, " cent ethyl alcohol, calcium carbide, benzene.

In a mortar powder and mix 2 grams Methane. and 1 gram of dry, fused sodium acetate. With the mixture half fill an ignition tube 15 cm. long, and attach a delivery tube by means of a rubber cona.

of soda-lime

nector.

Support the tube horizontally, tap it to insure a passage for gas, and heat it with a moving flame. it is impure methane (cf. Collect the evolved gas 292)

Note its physical properties and After burning a test tube of the gas, combustibility. lime-water into the tube, close it with the thumb, pour and shake it. Result? Conclusion? To one test tube
three test tubes.

- in

methane add a drop of bromine water. Close the Does the color of the bromine tube, and shake it.
of

disappear?
c.c.

In a 100 c.c. flask cautiously add 10 Ethylene. of concentrated sulphuric acid to 5 c.c. of alcohol. Shake the flask after each addition of acid so as to insure
b.

Support the flask over wire gauze but not quite touching it, and attach a stopper and a delivery tube with a rubber connector. Do not leave the delivery tube in the
mixing.

ETHYL ALCOHOL.

HI

water when you stop heating! Heat with a small flame until a regular stream of gas comes off, and collect three
test tubes full over water.

Note

its

physical properties

and the character bromine water as


Acetylene. of water with 5
c.

of its flame. in a.

Test with lime-water and


c.c.

Results?

In a test tube mix 2


c.c. of

no more
pieces of cal-

alcohol.

Add two

cium carbide the

size of peas,

and

at once attach a stopper

and delivery tube.


directed in a
d.

Collect the evolved gas (acetylene) over water in three test tubes. Note its properties as

and

b.

Do

not inhale

it.

Benzene.
odor.

Put

half
6

cubic

centimeter
dish.

more
its

of benzene,

6,

in

an evaporating

no Note
its

Carefully ignite the benzene.

Describe

flame.
zene,
if

Write the equation for the combustion of benthe products are carbon dioxide and water.

EXPERIMENT LXXX.
ETHYL ALCOHOL.
Apparatus.
Materials.

Flask (100

c.c.),

stopper and delivery tube,

test tubes, evaporating dish, distilling apparatus.

Molasses (or
(or

lime-water
alcohol,
a.

baryta

powdered
25
c.c.

water), litmus, shellac or rosin.

powdered grape sugar), yeast, sodium bicarbonate,

To

lasses or

add 5 c.c. moone cubic about and powdered grape sugar


water in a 100
c.c. flask

centimeter

Attach tightly a of compressed yeast. the tube pass into let and a with delivery tube, stopper Let the tube. a test in water or 5 c.c, lime-water baryta

112
flask

LABORATORY EXERCISES.
stand in a

warm

place,

and note

results.

If

you

leave the delivery tube in the lime-water over night, see that it dips only slightly below the upper surface of

the liquid. Why? If the test tube contains no prethe next cipitate day, heat its contents to boiling. Exthe result. Test the reaction of the solution in the plain
flask
b.

toward litmus.

Result?
to collect from several students the

Ask the teacher


was not done

they have prepared, and to distill it, if in connection with 280. If the first of the distillate do not burn a flame is when portions must be redistilled. The first few drops applied they then be tested for alcohol. may
dilute alcohol
this
c.

Set

some

of the fermented solution aside, without

stoppering the flask, for a week or two. Then note the taste of the solution, its reaction to litmus and its effect

upon a
Results?
d.

little

solid

sodium bicarbonate

in a test tube.

of alcohol into an evaporatthe dish ing dish, slightly, and apply a flame. Note the color of the alcohol flame. Write the equation for its combustion.

Put two or three drops

warm

e.

Treat half a cubic centimeter of powdered shellac

or rosin in a test tube, with 5 c.c. alcohol. Close the tube with the thumb, and shake it. Result? Add 5
c.c.

water.

Result?

Let the tube stand until the next

period.

Result?

ALDEHYDES.

EXPERIMENT LXXXI.
ETHYL ETHER.
Apparatus.
Materials.

Evaporating dish, test tubes. Ethyl ether, paraffin.

Caution.

Do

not bring the bottle of ether near a flame!

a. Put two drops of ether into an evaporating dish, remove the ether bottle, and apply a flame to the ether

in the evaporating dish. Describe the flame. b. In a test tube add 2 c.c. ether to a piece of paraffin half the size of a pea, shaking. Result? Pour the ether

out into the evaporating dish, and hold the dish in the hand to drive off the ether. Result? Note the volatility

and odor

of the ether.

EXPERIMENT LXXXII.
ALDEHYDES.
Apparatus.
tongs. Materials.

Test tubes, stirring rod, ring stand or rack,

Granular potassium dichromate, concentrated sulphuric acid, methyl alcohol, ethyl alcohol; solutions of silver nitrate, caustic soda, and ammonia; copper wire for spiral.
a.

In a test tube add 2


c.c.

acid to 6

and add
c.c.

c.c. of concentrated sulphuric of water, cool the mixture under the tap, 2 c.c. of alcohol. Pour this mixture upon 2

of granular potassium dichromate in a test tube.

114
Hold the

LABORATORY EXERCISES.

test tube over the sink. Results? Note the odor of the escaping vapors of acetaldehyde, CH 3 CHO. Hold in the vapors a stirring rod wet with ammoniacal To make this, add one drop of a silver nitrate solution. 10 per cent solution of caustic soda to 1 c.c. of silver nitrate solution, and then add 1 c.c. of ammonia water. The deposit on the rod is silver. Explain. 6. Put 2 c.c. of methyl alcohol, CH 3 OH, in a test tube supported in a ring stand or rack. Make a copper

glass rod or a pencil a foot of wire. Remove the copper pencil or rod, and hold the in the flame Then (use tongs) until it is red hot. spiral
spiral

by winding about a

drop

it

into the methyl alcohol.

of formaldehyde, alcohol.

CH O,
2

Note the sharp vapor mixed with the vapor of the

CHaOH+O

CH 0+H 0.
2

EXPERIMENT

LXXXIII.

ACETIC ACID AND ACETATES.


Apparatus.
Materials.

Beaker (50

c.c.), test

tubes, evaporating dish,

stirring rod, wire gauze, ring stand.

acid, concentrated sulphuric acid, vinegar,

Commercial (concentrated and dilute) acetic sodium carbonate,


papers, alcohol.

litmus and

filter

a. Note the taste of a drop of dilute acetic acid. Heat some to boiling in a test tube. Odor? Its action to litmus? Cf. Experiment XXIV, a and 6. Test vinegar in the same ways. Results? b. In a test tube mix 1 c.c. of concentrated acetic acid with 2 c.c. of alcohol, and add half a c.c. of concen-

OTHER ORGANIC ACIDS.

115

odor.

trated sulphuric acid. Heat carefully, and describe the It is that of ethyl acetate, The 3 COOC 2 5

CH

Equation? If you were sulphuric acid removes water. given a liquid suspected of being acetic acid, how would you prove it to be this substance?
c.

In a 50

c.c.

carbonate in 10 c.c. of water


acetic acid (5
c.c.,

beaker dissolve 10 grams of sodium and add to it commercial or less, at a time) until the reaction is

distinctly acid on stirring, and effervescence ceases. Then transfer the solution to an evaporating dish, and concentrate it over the wire gauze until a drop held on a
stirring

rod
g).

crystallizes

when

cool

(cf.

Experiment

XXXVII, Name the


d.

Set the dish aside until the next period.

crystals.

Their shape?

Filter

them

off,

and

dry them between

papers. Carefully heat some of the crystals of c in a test tube. Do they contain crystal water (cf. Experiment XVII)? Treat 1 c.c. of them, in a test tube, with 1 c.c. of con-

filter

Result? centrated sulphuric acid, and warm gently. Odor? Remember to pour the concentrated acid into

water when cleaning the test tube

the crystals add 1 c.c. alcohol and half a Warm gently, and c.c. of concentrated sulphuric acid. note the odor of the vapors. Result? Conclusion?

To

1 c.c. of

EXPERIMENT LXXXIV.
OTHER ORGANIC
Materials.
acid,

ACIDS.
oxalic acid,

Citric acid,

lemon

juice,

benzoic

alcohol, sodium bicarbonate, potassium permanganate

solution, dilute

and concentrated sulphuric

acid, litmus,

116
a.

LABORATORY EXERCISES.
For the properties of
tartaric acid see

Experiments
1

XXIV, c; XL VII, a; LX, c; and LXI, b and c. 6. Make an aqueous solution (by heating) of
or
less,

gram,

of crystallized citric acid,

HsCeE^OT+H^O, and

its taste, odor, and reaction toward lilmus and toward sodium bicarbonate. Repeat, using lemon juice

note

instead of citric acid solution.


c.

Results?
for

See

Experiment

LXXVIII
heated.

the

behavior

of

oxalic acid,

HCO
2
2

4,

when

water in oxalic acid. permanganate solution add half a c.c. of dilute sulphuric Reacid and then oxalic acid solution, drop by drop.
of crystal
sult?
d.

Prove the presence To 1 c.c. of potassium

Conclusion?

Heat

1 c.c. of

of water.

Result?

benzoic acid, C 6 5 COOH, with 5 c.c. Odor of vapors? Boil for a moment.

Now cool the solution

under the faucet.

Result?
its

Redis-

solve the benzoic acid

by applying

heat.

Cautiously

taste a drop of the solution,

and note
1
c.c.

action toward

litmus and sodium bicarbonate.

Results?
of benzoic acid

In a test tube heat carefully


with
half
1 c.c. of alcohol

until

you

c.c.

of

concentrated

get a solution; then add sulphuric acid and heat

again.

Note the odor of the vapors of ethyl benzoate, C6H 5 COOC 2 H5. Pour the solution into 10 c.c. water, and note the separation of the oily ester.

EXPERIMENT LXXXV.
SOAP.
Apparatus.
stand.
"

Tin

"
can,
stirring

rod,

test

tubes,

ring

SOAP.

117

Materials. Sodium hydroxide, lard, fine salt, " Castile " or " soap, litmus, dilute sulphuric acid, calcium sulphate solution.

"

Ivory

In a clean " tin " can dissolve 8 grams of sodium hydroxide in 60 c.c. cold water. If possible have the cover only partially cut out, so that it may be pushed down as a lid during the boiling. To the alkaline solua.

tion

add 25 grams of lard, and heat the mixture to boiling, having the opening of the can almost closed by the lid.
careful not to let the alkali spatter into your eyes! After thirty minutes stop the boiling, and see if the mixture begins to become solid. (Care !) If not, continue

Be

Beating until

it

does.
it is

Now
grams

add to the mixture, while


of fine salt in lots of

still

warm, 16

about 2 grams each. Stir carefully after each addition. Finally, boil the mixture for ten minutes, and let it cool. The soap will appear as a solid cake on the surface of the solution. Remove it, rinse it with a little water, and let it dry. " " " " 6. Dissolve about 1 c.c. of Castile or Ivory soap in 10 c.c. of water, and test the reaction of the Result? Treat half of the solusolution with litmus.
tion

with dilute sulphuric acid.

Result?

The

solid

product is a mixture of the organic acids of the soap. Treat the other half of the soap solution with a soluResult? Heat to boiling. tion of calcium sulphate. The product is the calcium salt of the acids (" lime (Cf. 70, 413, and 435 of text.) soap ")

118

LABORATORY EXERCISES.

EXPERIMENT LXXXVI.
CARBOHYDRATES.
Apparatus.
Materials.
sugar,

Fehling's

Beaker, test tubes, ring stand, wire gauze. solution (see a), grape sugar, cane

molasses, concentrated hydrochloric acid, sodium carbonate, starch or starch paste.

a. See Experiment LXIX for the action of grape sugar with alkaline cupric salts. A better solution for testing " the sugars is the one called Fehling's Solution."

Cupric sulphate crystals (34.64 grams) and

1 c.c. dilute

sulphuric acid are dissolved in water, and the solutio'n This is solution I. Soluis diluted to exactly 500 c.c.
tion II consists of 175 grams of sodium potassium tartrate,

to

make

50 grams of sodium hydroxide, and enough water These solutions the volume exactly 500 c.c.

are kept in separate, rubber-stoppered bottles. Equal volumes of the two are mixed just before they are used.

One

cubic centimeter of Fehling's solution is completely reduced by exactly 0.005 gram of grape sugar. To 10 c.c. Fehling's solution in a beaker add a drop of a solution of grape sugar, and heat to boiling over the wire
gauze.

Result? Let the precipitate settle, and add another drop of grape sugar solution; repeat the process until the Fehling's solution has just lost its blue color. Calculate how much grape sugar you added.
b.

In a test tube add some cane sugar solution to 5

c.c.

Is there Fehling's solution, and heat to boiling. reduction? Try a solution of molasses instead of cane

sugar.

Result?

PRINCIPLES OF QUALITATIVE ANALYSIS.


c.

119

To 20

c.c.

cane sugar solution in a beaker add 2

of concentrated hydrochloric acid, and heat gently to boiling for fifteen minutes over the wire gauze. Cool,
c.c.

and neutralize the acid with solid sodium carbonate; then test with Fehling's solution. Result? d. Repeat b and c, using 20 c.c. starch solution (make it as in Experiment LI, d) instead of cane sugar. Results?

EXPERIMENT LXXXVII.
SOME PRINCIPLES OF QUALITATIVE
Apparatus.
Materials.

ANALYSIS.

Funnel, funnel support, beaker, test tubes. Solutions of nitrates of iron (ferric), silver,

and sodium; hydrochloric acid, hydrogen sulphide, dilute sulphuric acid, ammonia water, filter papers, and " two or more " unknown substances.
copper, barium,

a system of experiments for the separation and identification of the elements present In a limited sense the term in mixtures of substances.
a.

Qualitative Analysis

is

applied to the detection of the ordinary metals and The separation of metals present as ions in a acids. solution is possible if we can convert some of the metals into insoluble compounds while leaving the others in
is

solution.

The

following

scheme

of analysis

may
of

experiments show how a be devised for the separation of

the five metals:

copper, iron, barium, and sodium. the We use solutions nitrates, since these are all in the Make soluble. ferric nitrate, if this is not found or wire iron of 1 about gram laboratory, by covering
silver,

filings

with 10

c.c.

of water in a beaker

and adding 10

120
c.c.

LABORATORY EXERCISES.
dilute nitric acid in small portions.

When

action

ceases, filter the solution and dilute it to 60 c.c. b. To 5 c.c. of each of the nitrates named in a

add
at

dilute

time

one hydrochloric acid until there is an excess.

cubic

centimeter
if

excess of the precipitant let

you have an the precipitate settle, and

To know

add a drop more


or
filter

little

of the precipitated solution

of the precipitant to the clear solution; and test the

filtrate

in the

graphs.)

Be

same way. 246, last two para(Cf. sure that your test tubes are clean for

every

test.

Copy the following table in your note book, and put down the results in their places.
Effect of

PRINCIPLES OF QUALITATIVE ANALYSIS.


e.

121
in

Repeat

d,

using

ammonium

hydroxide solution

place of sulphuric acid. tabulated in b to e devise a plan /. From the result? for identifying any one of the five nitrates, and of

separating them,

if

they are

all

present in a mixture.

previous experiments tell hgw you would g. determine whether a white, soluble solid given you was

From

sodium
h.

chlorate,

nitrate,

sulphate,

carbonate,

sulphite,

acetate, or thiosulphatef

If

barium

Why
if

you wished to make a mixture of copper and Why? salts, would you use copper sulphate? not use barium chloride or ferric chloride solution

you wish to get a soluble mixture of the ions of these metals and those of silver? i. Get from the teacher two or more unknown substances, and determine what metal or metals of the five

named

are present

also

what

acid.

UNIVERSITY OF CALIFORNIA LIBRARY BERKELEY


Return
This book
is

to desk

from which borrowed.

DUE on the last date stamped below.

RECEIVED
MAR

16 '69 -6PM

LOAN DEPT.

16Dep'52S5

1952 LU

LD

21-100TO-9,'47(A5702sl6)476

YC 22078

Q&3I
UNIVERSITY OF CALIFORNIA LIBRARY

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