rness

& J. Lambert

A New
Certificate

ourth Edition
 VI

Group number
1 2 3 4 5 6 7
1008 4003
H He
Hydiogen Helium
i
PERIODIC TABLE OF ELEMENTS 2
6 939 9 012 10 811 12-011 14007 15999 18998 20-183

Li Be B C N F Ne
Lithium Beryllium Boron Corbon Nitrogen Oxygen Fluorine Neon
3 4 5 6 7 8 9 10
22 990 24 312 26982 28 086 30 974 32 064 35453 39 948
No Mg Al Si P S CI Ar

Sodium Mognesium Aluminium Silicon Phosphorus Sulphur Chlorine Argon

11 12 13 14 15 16 17 18

39 102 40 080 44956 47-900 50942 51996 54 938 55-847 58933 58 710 63 540 65 370 69720 72 590 74-922 78-960 79909 83800
K Co Sc Ti V Cr Mn Fe Co Ni Cu Zn Go Ge As Se Br Kr
Potassium Calcium Scandium Titonium Vonadium Chromium Mongonese Iron Cobalt Nickel Copper Zinc Gallium Germcnium Arsenic Selenium Bromine Krypton
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
85170 87-620 88 905 91220 92906 95940 [99] 101-070 102 905 106-400 107 870 112 400 114820 118 690 121750 127-600 126904 131 300
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Polladlum Silver Codmium Indium Tin Antimony Tellurium Iodine Xenon
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
132905 137 340 138 910 178-490 180-948 183850 186200 190-200 192 200 •95090 196967 200 590 204-370 207190 208 980 [210] [210] [222]

Cs Bo La Hf To W Re Os lr PI Ad Hg Tl Pb Bi Po Al Rn
Coesium Barium Lonthonum Hofnium Tantolum Tungsten Rhenium Osmium Iridium Plotinum Gold Mercury Thallium Leod Bismuth Polonium Astatine Rod on
55 56 57 72 ?i 74 75 76 77 78 79 80 81 82 83 84 85 86
[223] [226) 227*
Fr Ro Ac
Froncium Radium Actinium
87 88 89

138910 140120 140 907 144 240 [147] 150-350 •51-960 157 250 158924 162 500 164 930 167260 168 934 173040 174 970
Atomic weight
Lo Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Lanthanum Cerium Praseody- Neodymlum Promelhium Samorfun Europium Godolinlum Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
Symbol
57 58 59 rnium 60 61 62 S3 64 65 66 67 68 69 70 71

Nome 227* 232 038 [230 238 030 [237] [242] 1243] [247] [249] [251] [254] [253] [256] 254* [257]

Atomic number
Ac Th Po U Np Pu Am Cm 8k Cf Es Fm Md No Lw
Actinium Thorium Prolocfmium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelev- Nobelium Lowrencium
89 90 91 92 93 94 .95 96 97 98 99 100 101 ium 102 .03

[ ] This is the mass number of the Isotope with the longest Known half life of the element Indicated.
* Thit Is the most number of the most sloble or best known Isotope of the element indicated
 A New
Certificate
Chemistry
 BY THE SAME
School Certificate Chemistry
AUTHORS
A New
Graded Problems in Chemistry to Ordinary Level
(with ami without answers)
Chemistry
Certificate
Worked Examples and Problems in Ordinary Level
Advanced Level
A Class Book of Problems in Chemistry to
(with and without answers)

Simple Approach to Atomic Theory

A
Chemistry
Problems and Worked Examples in Chemistry to
Advanced Level
The Essentials of Qualitative Analysis

by
IN CONJUNCTION WITH DR F. SHERWOOD TAYLOR
The Essentials of Volumetric Analysis
A. Holderness m.Sc. f.r.i.c
BY A. HOLDERNESS
Formerly Senior Chemistry Master at
Intermediate Organic Chemistry Archbishop Holgate's Grammar School, York
Inorganic and Physical Chemistry
A Simple Approach to Organic Chemistry and
Revision Notes in Advanced Level Chemistry
Volume One. Organic Chemistry
Volume Two. Inorganic Chemistry
John Lambert m.Sc.
Volume Three. Physical Chemistry
Formerly Senior Chemistry Master at
BY J. LAMBERT King Edward's School, Birmingham

Tables for Elementary Analysis

BY T. MUIR AND J. LAMBERT

Practical Chemistry
FOURTH EDITION

HEINEMANN EDUCATIONAL
BOOKS LTD LONDON •
 Hcinemann Educational Books Ltd
LONDON EDINBURGH MELBOURNE TORONTO
SINGAPORE JOHANNESBURG AUCKLAND
NAIROBI HONG KONG IBADAN
NEW DELHI Preface to the Fourth Edition (1969)

ISBN 435 64408 4 (cased edn)

The developments now taking place constitute the greatest upheaval
ISBN 435 64410 6 Gimp edn)
in school chemistry teaching in living memory. The
problems it pre-
sents arc as great in text-book authorship as in teaching, including as
©A. Holderness and J. Lambert 1961, 1964, 1969 they do the implications of changing nomenclature and units as well
First Published 1961 as great modifications of syllabuses.
In the matter of nomenclature, we have adopted the Stock nota-
Second Edition 1961
tion for metallic compounds as well as the systematic naming of such
Reprinted 1962
groups as the oxides of nitrogen. At the same time, it has to be
Third Edition 1964 remembered that 'trivial' usages such as ferrous, ferric and cupric
Reprinted 1965, 1966, 1968 are found in all the English chemical literature before the 1960's and
Fourth Edition 1969 should be familiar to users of it. Consequently, these now obsolete
Reprinted 1970 forms are occasionally mentioned along with the revised usages.
such as red lead, lime, caustic soda,
Similarly, everyday 'trivial' terms
bicarbonate and others are mentioned in their place.
3
The SI system of units has been adopted, e.g., cm and dm for
8

volume measurements, except in a short section devoted to normality

(for historical reasons) when the litre (1) and ml units are retained.
Energy change is stated in terms of AH and kJ (with the equivalent
calorie figure at times). The mole unit is used frequently, though
with some trepidation about the ambiguity that could arise if our
young chemists use the term loosely. Terms such as gram-molecule
and gram-atom (though declared obsolete in some quarters) are
retained since they appear in the syllabus requirements of some
Boards. The banning of the term equivalent will probably come as a
jolt to older teachers, especially when it is substituted by an ex-
pression such as a mole of±Ht SOi. Enough of the historical develop-
ment of atomic theory has been retained to enable pupils to under-
stand that ia C =
12 is only a minor variation of convenience on the
older H= 1. The important experimental work formerly devoted to

Published by equivalents has been adapted to determine formulae of simple com-

Heinemann Educational Books Ltd
48 Charles Street, London W1X 8AH
Printed in Great Britain by
Butler and Tanner Ltd, Frome, Somerset
pounds and verify suitable equations. Atomic weight determination
is left to the mass spectrometer (with treatment suited to O-level).
The syllabuses of the examining Boards have, of course, a large
area of common ground but show some variations on the fringes.
The general emphasis of all Boards on such topics as periodicity,
VI PREFACE
electronic usages, molecular shapes, metallic
bonding, the Avogadro
constant and its relation to the mole, the pH
scale, elementary

chromatography, macromolecules (carbon, metals, starch, nylon),

kinetic theory and elementary organic chemistry, has been met by
the introduction or necessary expansion of these
topics. In addition, Preface to the First Edition
the fringe variations, e.g., London's requirements of polystyrene
some lithium and coppcr(l) chemistry and calorimetnc
and perspex,
measurements, or the Joint Matriculation Board's of the co-ordinate
social and economic considerations in
chemistry,
bond and some
have been taken into account. The new requirements of the
Hong A New Certificate Chemistry is designed as an alternative to the same

have also been satisfied by the in- authors' School Certificate Chemistry. The twenty-three years which
Kong Certificate of Education
oxidation number, have passed since the appearance of School Certificate Chemistry
clusion of its special topics, e.g., electroplating,
and the behaviour of hydrogen have brought inevitable changes in the science of Chemistry and in
lead accumulator, Leclanche cell
means, the substantial its presentation at middle-school level. Many of these changes have
chloride in toluene. It is hoped that, by this all
multiple been covered by alterations in the text of the book from time to
requirements of all the Boards have been met, including
supplied. time, but the electronic outlook which has developed in recent years
choice questions of which a practice set is
has made more decisive change and a new title desirable.
A. H. All the topics and many of the characteristics of the older book
November 1969
J. L. have been retained since they have proved, over the years, very
acceptable to teachers. Among these characteristics are the insistence
on adequate detail experimental work, a full presentation of
in
elementary molecular theory and chemical arithmetic, and plenty of
material for examination revision.
The principal features which justify the title, A New Certificate
Chemistry, are the treatment of oxidation-reduction and the relation
between metals and non-metals in electronic terms, wherever suit-
able. Similarly, topics such as the acid-base relation and
neutralisation are presented in ionic terms. These changes have
involved the introduction of ionic equations in much greater numbers
than before. At the same time, it has not been forgotten that ionic
equations do not lend themselves to calculations involving actual
compounds encountered in practical work. To meet this situation,
molecular equations have been retained in sufficient numbers and in
suitable contexts, so that firm contact is retained between equations
and calculations and the actual chemical materials which appear in
the stock bottles, the beakers and the filter-papers used by pupils in
chemistry. To this extent, A New Certificate Chemistry is a mixture
of the old and the new in middle-school chemistry. This, we hope, is
not unsuitable to the present transitional stage of development in
school science.

The authors have pleasure in acknowledging the very helpful

comments they have received, while preparing this book, from some
practising science teachers, more particularly Messrs A. B. Adamson,
vii
Vlll PREFACE
F. E. P. Alford, F. W. Ambler, H. G. Andrew, H. C. Cockroft,
E. H. Coulson, J. B. Guy, I. G. Jones, P. N. Lawrence, E. W. Moore,
T. A. Muir and J. Turpie.
They would also like to thank Mr E. Dickinson for his assistance
and advice at proof stage, and the eight School Certificate Examina-
tion Boards for permission to use their questions.
Contents
University of Bristol (B.). University of Cambridge, Local (C).
Central Welsh Board (C.W.B.). University of Durham (D.).
University of London (L.). Joint Matriculation Board (N.U.J.B.).
Oxford Local (O.)Oxford and Cambridge (O. and C).
Preface to the fourth edition V
Preface to the first edition vii
March 1961 A. H.
Chemical nomenclature xii
J. L. Physical and chemical change; elements, compounds,
mixtures 1

Atomic theory 12
Laws of combination by weight (experimental) 24
Atomic weight 33
The behaviour of gases under temperature and pressure
change 40
Experimental work on formula, reactions and equivalents 45
Calculations involving weights 54
Atomic structure; shape of molecules; kinetic theory;
periodicity 62
Molecular theory 95
Formulae of gases 112
Volumetric analysis 123
Electrochemical series and electrolysis 133
Types of reactions 153
Air, combustion and rusting 171
Water and solution 190
Acids, bases and salts 222
Oxides 242
Hydroxides 251
Hydrogen 263
Oxygen 272
Hydrogen peroxide and ozone 280
Carbon and its oxides; flame 287
Carbonates and hydrogen carbonates 309
Organic chemistry 319
Silicon and its compounds 348
Chlorine 355
Hydrogen chloride and the chlorides 366
Bromine and iodine 376
Sulphur 388
Hydrogen sulphide and the sulphides 395
Oxides and acids of sulphur; sulphates 403
Nitrogen and ammonia 423
IX
X CONTENTS
33 Nitric acid and the nitrates 435
34 Oxides of nitrogen 445
35 Phosphorus 455
36 Metals; extraction and uses; non-metals compared 463
37 Radioactivity; a brief account 498
38 Revision Notes 509 List of Plates
Definitions 524
General questions (including multiple choice) 528
Answers 531
Approximate atomic weights 532
Logarithmic tables 533 1 The Concorde facing page 18
International atomic weights 535
537 2 Atmosphere above a town 19
Index
3 (a) Water pipe blocked by deposits 56

(b) Stalagmites and stalactites 50

4 Atomic hydrogen used in welding 51

5 (a) Manufacture of carburetted water-gas 306

(b) Ammonia convertors 306

6 Manufacture and use of fertiliser 307

7 Blown glass 338

8 (a) Oslo evaporator 339

(b) Open-hearth furnace 339

xi
 CHEMICAL NOMENCLATURE X1U

the prefix hypo- with the -ous ending. An acid with a higher proportion
of oxygen than the -ic acid takes the prefix per- with the -ic ending.

Chemical Nomenclature
- -ite and per —
The corresponding salts have names of the form
ate. Thus
-ate, -ite, hypo

ACIDS SALTS
perchloric acid, HC10 4 . potassium perchlorate, KC10 4 .

chlor/c acid, HCIO3. potassium chlorate, KC10 3 .

chlorous acid, HC10 2 . potassium chlorite, KC10 2 .

THE word 'nomenclature' means 'system or scheme of naming'.

The following simple
hypochlorous acid, HCIO. potassium hypochlorite, KCIO.
treatment of chemical nomenclature will
enable you to state the composition of most chemical substances Notice also the following common pairs of acids and salts:
directly from their names.
ACIDS SALTS
ELEMENTS sulphuric acid, H S0
2 4. sulphates, e.g., Na 2 S0 4 .

The commonest elements have been known for a long time and
sulphurous acid,H 2 S0 3 . sulphites, e.g., Na 2 S0 3 .

there is generally no system about their naming. Recently isolated

nitric acid, HN0 3. nitrates, e.g., KN0 3.

nitrous acid, HNO a . nitrites, e.g., KN0 2 .

melals, however, have been given names ending in -ium or -urn, e.g.,
radium, platinum, osmium, duminium, while recently named non- A useful rule to remember is that a salt with the name ending -ate
metals have been given names ending in -on, e.g., argon, xenon. or -ite usually contains three elements, one of which is oxygen, e.g.,
lead sulphate, PbS0 4 , copper nitrate, Cu(N0 3 ) a, sodium hypo-
COMPOUNDS chlorite, NaClO. Note the two compounds, ferrous sulphide, FeS
Binary compounds (two elements), and ferrous sulphate, FeS0 4 (three elements includ-

The name-ending compounds containing only two

-ide is given to ing oxygen). These two are frequently confused by beginners.
elements and the nature of the elements is indicated in the two words
1 Recent recommendations of the Chemical Society and the Inter-
of the name, e.g., copper oxide, CuO; hydrogen sulphide, H 2 S. national Union of Pure and Applied Chemistry have made certain
The number of atoms of one of the elements contained in a mole- chemical names 'trivial' and they are to go out of use. Examples are
cule of the compound is sometimes indicated by a prefix to the second names in -ic and -ous derived from names of metals, e.g., ferric and
part of the name, e.g., carbon (//sulphide, CS 2 phosphorus rr/chloride, ferrous, cupric and cuprous. The recommended replacement takes the
;

PC1 3 carbon te/rachloride, CC1 4 phosphorus pentoxide, P 2 6

;
form of the ordinary name of the metal with its operative valency
; .

stated in brackets in Roman numerals. Where necessary, the majority

Acids and salts of the names have been changed to conform to
in the present edition
A great many acids contain hydrogen, oxygen and a third element, this notation. Some cases of the old usages have been left because
e.g., H,S0 4 , HN0 H P03, 3 4. The commonest and most stable of they occur in chemical literature before about 1960 and students
such acids usually highly oxidised and to it is given a name which
is should be familiar with them. Examples of change are the following:
ends in -ic and is derived from the element it contains in addition to
OLD NEW
hydrogen and oxygen, sulphuric acid,
e.g., H
2 S0 4 , and nitric acid,
HN0 Cuprous oxide CopperfJ) oxide, Cu 20.
3 An acid containing the same elements but less oxygen has the
.

name-ending changed to -ous, while one with less oxygen still takes Cupric oxide Copper(II) oxide, CuO.
1
Ferrous sulphate Iron (II) sulphate, FeS0 4 .
Hydroxides are exceptions to this rule but in these compounds the three
elements present are indicated in the name. Another exception is an acid Ferric sulphate Iron(IlI) sulphate, Fe^SO^.
salt of hydrogen sulphide, e.g. sodium hydrogen sulphide, NaHS, but here Plumbous chloride Lead(Il) chloride, PbCl 2 .
again the name is self-explanatory. In salts like ammonium chloride, NH.CI,
the NH, group has been treated as if it were an element.
Plumbic chloride Lead(IV) chloride, PbCl 4 .
xii
Manganese dioxide Manganese(IV) oxide, Mn0 2 .
 Chapter 1

Physical and Chemical Change

Elements, Compounds, Mixtures

PHYSICAL AND CHEMICAL CHANGE

THE science of Chemistry before
sets as primary
itself, its

the determination of the nature and properties of the non-

first,
objects,

living matter which surrounds us in that portion of the crust of the

earth to which we have and secondly, the preparation of new
access,
substances, scientifically interesting or generally useful, from the
materials which Nature has provided. In trying to determine the
nature of substances, chemists have been greatly interested in the
changes which these undergo when subject to conditions which they
normally do not encounter— high temperature, high pressure,
extreme cold, contact with other materials under varying conditions,
and so on. It is largely from the changes which materials undergo
when subject to these conditions that chemists, particularly in the last
150 years or so, have drawn conclusions about their nature.
But changes are multifarious. Some of them do not interest the
scientist, as such, at all. The change wrought when the hand of an
artist transfers paint from palette to canvas and, spreading it in a
particular way, creates a work of art, is a matter of jesthetics, not of
science. Any one change may be viewed from many different angles.
When iron rusts, a chemist is concerned with the different properties
which the iron and rust possess. How
does each react with acids,
alkalis and other reagents? He also tries to give an explanation of what
occurred to the iron when it rusted. The physicist will want to know
whether the density, the conductivity and the specific heat of the rust
are the same as that of iron, from which it has been made. An
economist thinks of the huge cost which accompanies the change, for
millions of pounds are spent yearly in an endeavour to prevent iron
from rusting. It may be that what the chemist and the physicist find
out about the rusting of iron will help the economist (or, more
directly, the manufacturer of iron articles). It is mainly as a result of
2 A NBW CERTIFICATE CHEMISTRY PHYSICAL AND CHBMICAL CHANGE
smell or, you prefer some less
if
chemical research that rustless and stainless steels have appeared,
commonplace evidence, by burning
while during that research, the physicist has been careful to ensure the sulphur in a gas-jar and adding
that the elasticity and tensile strength of the steel have not been im- to the jar some blue litmus solution.
paired by the process which made them rustless. Clearly, we must The gas, sulphur dioxide, will turn
red.
attempt to define, if only roughly, the kind of changes in which the it

chemist is interested and to which the name 'chemical' can properly

be applied. With the object of attaining some kind of definition of A little consideration will quickly show that the six changes we
'chemical changes', we will now examine a few changes in the hope
have considered above are not all the same in nature. They fall,
actually, into two classes, which are distinguished by the following
that, from them, some conclusions may emerge.
peculiarities.
1. All the changes in the right-hand column were easily reversible;
Hold one end of a piece of
1. Repeat the experiment with
platinum by holding a loose coil of
the molten sulphur returned to the solid form when cooled; the
magnesium ribbon in tongs and
platinum wire in a Bunsen flame. platinum wire ceased to glow and regained its original appearance
put the other end in a Bunsen
flame. Note the intense brilliance Note the white-hot glow of the when removed from the flame; the common salt was recovered by
of the flame of the burning mag- metal, but contrast its unchanged evaporating off the water. Contrast these results with those of the
nesium and the nature of the appearance, after cooling, with the
changes in the left-hand column. The white ash from magnesium
—
residue a white ash which re- — white ash left by the magnesium.
was totally unlike the original magnesium, and it would be a difficult
mains.
matter to obtain magnesium from it; on evaporation of water in
2. Take a small piece of sodium To distilled water in a beaker, Experiment 2, we recovered not sodium, but caustic soda, from which
in tongs from the oil under which add some common salt and stir the sodium cannot easily be obtained; the sulphur became part of a gas
it is kept, and, never touching it mixture. The common salt under-
from which it would be difficult to recover sulphur. These changes
with your fingers, cut it into pieces goes an obvious change; it gradu-
ally disappears forming a solution are not reversible. The easily reversible type of change is called
about the size of a very small pea.
Drop these pieces in turn on to the and being no longer visible as a 'physical change*; the more permanent type 'chemical change'.
surface of a little distilled water in a white solid. Put the liquid into a 2. In none of the physical changes recorded in the right-hand
small beaker. Note how the sodium porcelain dish and heat gently
column was a new kind of matter formed we began with platinum,
;

melts into a ball, darts about the until all the water has evaporated
off. The common salt reappears in
common salt and sulphur and, after the change, finished with just
surface of the water, produces a
hissing sound and finally disappears its original white solid form. those materials. In all the chemical changes recorded in the left-hand
with a small flash and explosion. column, some new kind of matter was formed: magnesium was con-
Heat the resulting clear liquid on verted to the white powdery ash, magnesium oxide, sodium to caustic
an iron dish until no more steam
is given off. On cooling, a white
—
soda and solid sulphur to the gas, sulphur dioxide a new kind of
added to water, this matter each time. This is characteristic of chemical change.
solid is left. If
solid dissolves but does not show 3. The physical changes in the right-hand column were not accom-

the same vigorous action as sodium. panied by any marked external effects. The solution of common salt
It is a new substance, caustic soda. in water and the melting of sulphur were not violent changes. The

Powder some sulphur in a action of sodium with water, however, produced enough heat to melt
3. Heat some roll sulphur on a roll

deflagrating spoon. Note how the
sulphur melts and later begins to
burn with a blue flame. It gradually
decreases in amount and
spoon will empty. The
be left
sulphur has not simply been anni-
hilated. Its disappearance is due to
its conversion into a new gaseous
substance which is invisible, but
whose presence in the air can be
detected merely by its irritating
mortar, then heat gently in a test-
it
tube, shaking all the time. Notice
how the sulphur melts to an amber-
finally the coloured liquid (other changes will
occur if it is more strongly heated)
and that this liquid, on cooling,
returns to its original condition as a
yellow solid.
the sodium and was violent enough to be slightly explosive at the
end; the burning of magnesium produced intense heat and light, and
the burning of sulphur similar, but less intense, effects. The chemical
changes were the more violent, and were accompanied by heat
changes. This is commonly the case.
4. We carried out no weighings during our experiments, but it
could actually have been shown that, in all three physical changes
which we recorded on the right, no change of weight occurred; the
sulphur, platinum and common salt weighed just as much before the
 NEW CERTIFICATE CHEMISTRY ELEMENTS, COMPOUNDS, MIXTURES
4 A

changes as after them. In the three chemical changes, however, it PHYSICAL CHANGE CHEMICAL CHANGE
would have been found that the white ash weighed more than the Is generally not easily re-
1. Is generally easily reversible 1.
magnesium, the caustic soda more than the sodium and the gaseous versible
sulphur dioxide more than the sulphur. (These gains in weight are Produces no new kind of 2. Always produces a new kind
2.
made at the expense of other materials which lose in weight corre- matter of matter
spondingly; the gains in the case of magnesium and sulphur were usually accompanied by
3. Is not accompanied by great 3. Is
made at the expense of the air and, in the case of sodium, at the heat change (except latent considerable heat change
expense of the water.) accompanying
—
thus distinguish two kinds of changes chemical changes and
We
heat effects
changes of state)
physical changes. 4. Produces no change of weight 4. Produces individual sub-
Now consider the following suggestions about a few common stances whose weights are diff-
changes and decide by comparison with those discussed above erent from those of the original
whether the changes are physical or chemical. The correct classi- individual substances
fication appears on p. 5. Thus, if two substances, A
and B, react chemically and
1. Melting of ice; (b) conversion of water to steam.
(a) are changed into substances
Are the changes easily reversed? Are there any noticeably violent C and D, the weight of C
external effects? will be different from the

Burning of coal.
2.
weight of A or B, and the
the coal appear to weigh the same as the products after burn-
Does weight of Dwill be different

ing it? (Appearances here are deceptive, see p. 25.) Can we easily
from the weight of A or B.
obtain coal again from its products of combustion? Are there any Examples Examples
noticeable external effects while coal is burning? 1. All cases of the melting of a 1. The burning of any substance
solid to a liquid (or the re- in air
3.Rusting of iron.
verse)
Can iron be easily recovered from the rust?
2. All cases of vaporisation of a 2. The rusting of iron
Magnetising iron.
4.
liquid (or the reverse)
Can the iron be readily de-magnetised? Are there any marked 3. Magnetisation of iron 3. The slaking of lime
changes during magnetisation? 4. The heating of a metal wire 4. Explosion of coal-gas or hy-
5. A coal-gas explosion. by electricity drogen with air
Is this change violent? Is there considerable heat change?

6. Heating of the filament of an electric light globe by the current.

Is the filament readily cooled again? Does it appear changed
when ELEMENTS, COMPOUNDS, MIXTURES
cooled ? Elements and Compounds
7. The melting of candle-wax. We begin our study of elements and compounds by consider-
will
Is the liquid wax easily solidified again? Docs itthen appear the ing two simple chemical changes.
fairly
same as the original wax? Are there any marked heating effects as 1. Put a little red oxide of mercury (mercuric oxide) into a dry test-

the melting occurs? tube. Heat it, rotating the test-tube so that it does not become mis-
shapen. A
silvery mirror gradually appears on the upper part of the

We may now summarise the characteristics of chemical and test-tube (where it is cool), and later silvery globules of mercury will

physical change in the table, p. 5. be seen. When the mirror begins to appear, insert a glowing splint
of wood into the test-tube. It is rekindled. This is because the in-
visible gas, oxygen, is coming off from the heated oxide.
6 A NEW CERTIFICATE CHEMISTRY ELEMENTS, COMPOUNDS, MIXTURES 7

made up of two or more elements combined together. They are

It is clear that, under the action of heat, mercuric oxide has yielded
called 'compounds'. astounding to reflect that all compounds
It is
two products —mercury and oxygen.
2. Repeat the above experiment, using lead nitrate. Brown fumes on the earth, from the simplest, which, like water, contain only two
are given off in this case (they are called nitrogen dioxide), and, by
elements, to those complex materials of which our own bodily tissues

the test given above, it can be shown that oxygen is also liberated. are composed, are made from about one hundred simple, elementary
materials. The elements are indeed a small select band.
Finally a yellow solid will remain in the test-tube. This solid is

litharge.
There follows a short list of common compounds and the elements
These experiments show that both mercuric oxide and lead nitrate which compose them.
must be fairly complex substances. This is obvious from the fact that
mercuric oxide yielded, under the action of heat, two substances,
COMPOUND ELEMENTS CONTAINED
mercury and oxygen, while lead nitrate yielded three litharge, — Water Oxygen; hydrogen
nitrogen dioxide and oxygen. The question now arises whether Sugar Oxygen; hydrogen; carbon
these products can themselves be split up further into still simpler Common salt Sodium; chlorine
substances. The answer to this question is that in two cases they Saltpetre Potassium; nitrogen; oxygen
can; from litharge we can, by suitable chemical means, obtain lead Marble Calcium; oxygen; carbon
and oxygen, and from nitrogen dioxide, nitrogen and oxygen. This Blue vitriol Copper; sulphur; oxygen; hydrogen
means that litharge and nitrogen dioxide are themselves complex Oilof vitriol Hydrogen; sulphur; oxygen
substances. How much further can this process of splitting up into Sand Silicon; oxygen
simpler products be carried? Can we obtain from the lead, nitrogen, Clay Aluminium; silicon; oxygen; hydrogen
oxygen and mercury, into which we have resolved our original lead
nitrate and mercuric oxide, any substances which are simpler still? (Note how commonly oxygen occurs; it is the most widely dis-
The answer now is that we cannot. By no chemical process whatever tributed of all the elements.)
is it possible to obtain from lead, mercury, oxygen or nitrogen any We may now define a compound.
substance simpler than themselves. Clearly, these four simple sub- Definition. A compound is a substance which contains two or more
stances are different from the more complex mercuric oxide and lead elements chemically combined together.
nitrate. The number of substances which like lead, oxygen, mercury We have found it necessary to use the expression 'chemically com-
and nitrogen, are incapable of being split up into simpler substances bined'. The meaning of it is connected with the idea of chemical
is small. There is very good reason to believe that about a hundred change which was discussed earlier. We must now try to obtain a
such substances may exist, and, of them, nearly all are actually known clearer idea of the meaning of the expression and, to do this, we shall
on the earth. To them the name 'elements' has been given. We may contrast the properties of mixtures and compounds in the work of
now define this term. the next section.
Definition. An a substance which cannot by any known
element is

chemical process be split up into two or more simpler substances. Mixtures and Compounds
A list of the elements is given on p. 535. We
may here mention a
Weigh out 28 g of iron filings and 16 g of sulphur (any multiples
—
few of the commoner ones. All the metals lead, zinc, iron, copper,
or fractions of these weights will do equally well). Grind the two
tin, —
platinum, gold, silver and the rest are elements; so also are the
thoroughly in a mortar and put about half of the mixture into a dry
oxygen and nitrogen of the air, together with carbon, sulphur,
test-tube. Heat the test-tube, at the bottom, with a small flame. The
phosphorus, iodine and others to the number of over one hundred.
mixture will glow. When it docs so, remove the flame, and hold the
Remember the characteristic they all possess - they cannot by any test-tube over a mortar as a precaution against breakage. The glow
known chemical process be made to yield substances simpler than will then spread slowly through the mixture without further heating.
themselves.
Allow the test-tube to cool, then break it away from the mass of
From this small band of elements, all other substances on the earth
material left. A dark grey, almost black, solid will be found.
are made. The number of chemical substances known is more than a
In the following experiments, we shall compare the properties of
million and a half. All of these, except the elements themselves, are

8 A NEW CERTIFICATE CHEMISTRY
of the black solid
the original mixture of iron and sulphur with those
left after heating it.
Experiment Mixture before heating
Action with Place enough of the
I.
mixture in a test-tube to
water
fill about 2-5 cm of its
depth. Half fill the test-
tube with water, shake it
well, then allow the test-
tube to stand. The denser
iron will settle more
rapidly than the lighter
sulphur and form a layer
below it. The experiment
separates the iron from
the sulphur.
Rub one end of a bar
2. Action of a
magnet magnet well into the mix-
ture, raise it and
gently. The
iron filings
will have been attracted
by the magnet and will
adhere to The sulphur
it.
will not. They are sepa-
rated.
Half fill a test-tube with
3. Action with
carbon carbon disulphide, add
disulphide some of the mixture and
shake for a few minutes.
Filter the mixture through
a dry filter-paper and
funnel on to a dry clock-
glass. Allow the filtrate to
evaporate to dryness (in a
fume-chamber) at the or-
dinary temperature. On
the clock-glass, a yellow
deposit of solid sulphur
will be left. The carbon
disulphide has dissolved
out the sulphur from the
mixture and so separated
it from the iron.
4. Action of Add dilutchydrochloric
acid to some of the mix-
dilute hydro-
ture in a test-tube.
chloric acid
gently. There is rapid
effervescence. Apply a
lighted taper to the test-
Solid left after heating
Carry out the same test.
The solid settles as a
single layer with no sign
of separation of the iron
from the sulphur.
Repeat with the other
end of the magnet. A very
iron (left unattacked
tap little
by the sulphur) may be
attracted by the magnet
but it will be very much
less than before. The bulk
of the iron is not attracted
from the black solid and
is not separated from the
sulphur.
Repeat the experiment
described opposite. A
very slight deposit of
sulphur (left unattacked
by the iron) may remain,
but the great bulk of the
sulphur has not been
separated from the iron.
Repeat the experiment
described opposite. Effer-
Warm vescence occurs again.
Apply the following two
tests to the gas:
1. Smell very cau-
ELEMENTS, COMPOUNDS, MIXTURES 9
Experiment Mixture before heating Solid left after heating
tube. Theresulting slight tiously. The
rather dis-
explosion shows that the gusting smell is similar to
gas is hydrogen. The iron that of rotten eggs.
has reacted with the acid 2. Apply a lighted
The
to produce this gas. The taper to the test-tube.
sulphur remains un- gas burns with a blue
changed. flame but without explo-
sion. It iS HYDROGEN
SULPHIDE.
Reason for the above Differences of Properties
and
It is clear that the solid left after heating the mixture of iron
sulphur differs greatly in properties from the original mixture itself.
1. Before the heating, the iron could be separated from the sulphur
by physical methods. For example, by shaking with water, we
took advantage of the physical property of density to separate the
denser iron from the lighter sulphur; we also separated the iron from
the sulphur by using its physical magnetic properties and by physical
solution of the sulphur in carbon disulphide. In none of these experi-
ments was any chemical action involved, but these physical methods
could not separate the sulphur from the iron after the mixture had
been heated. Physical methods of separation were then useless.
2. Again, in the mixture before heating, the two elements clearly
exercised their own independent properties. The iron was attracted
by the magnet just as it would have been if the sulphur had not been
present; the sulphur dissolved in carbon disulphide without inter-
ference from the iron. Similarly, during the action of dilute hydro-
chloric acid on the mixture, the iron reacted with the acid exactly as
if no sulphur were present, while the sulphur itself remained un-
changed. After the heating, however, the black solid left showed
properties of its own. The sulphur present in it was no longer dis-
solved out by carbon disulphide nor was the iron attracted by a
magnet, while the separate densities of the two elements were no
longer available for use in their separation. The action of dilute
hydrochloric acid gave an entirely different reaction, with evolution
of hydrogen sulphide instead of hydrogen. So we see that during the
heating the separate properties of the iron and sulphur were lost and
the new properties of the black solid, ferrous sulphide, appeared.
The reason for this difference is that before the heating the two
elements were simply mixed together, while during the heating they
underwent chemical combination, forming the compound, ferrous
sulphide. As a result of this change, the elements were united by a
chemical link or bond instead of being merely close together in space.
10 A NEW CERTIFICATE CHEMISTRY QUESTIONS 11

The nature of this bond has been the object of much speculation, and experiments in support of your views. How could metallic sodium be
it is now known to be electrical. recovered from the liquid? (N.U.J.B.)

Another characteristic difference between physical mixing and

3.
chemical combination is apparent from this experiment. During the
mixing of the iron and sulphur in the mortar, no change was observed
except a kind of averaging of the colours of the two elements so that
the mixture had a colour between the grey of iron and the yellow of
sulphur. During the chemical combination, however, enough heat
was given out to raise the whole mass to a bright red glow, once the
action had been started by the external application of heat. Chemical
combination is often accompanied by heat changes of this kind, but
physical mixing is not.
4. A and most important difference between mixtures and
further
3. What is the essential difference between a chemical and a physical
change?
Indicate clearly the chemical and physical changes involved in the follow-
ing processes, giving full reasons in each case: (a) the addition of metallic
sodium to water; (/>) the solution of sodium chloride in water; (c) the
heating of magnesium in air; (</) the heating of ammonium chloride; (e) the
addition of water to concentrated sulphuric acid. (L.)
4. Describe the experiments you would carry out in seeking to determine
whether a given white powder is a pure substance or a mixture. If the
substance is a pure chemical compound, how would you propose to
ascertain whether it is (i) a salt; (ii) a basic oxide, or (iii) a peroxide?
(N.U.J.B.)
5. Illustrate three differences between metallic and non-metallic

chemical compounds is that the composition of a compound by elements by reference to the properties of iron and sulphur. Describe
three tests by means of which you would prove that the compound, iron
weight is fixed and unalterable, while that of a mixture may vary sulphide, formed by heating a mixture of iron filings and sulphur, differs
within wide limits. For example, pure ferrous sulphide always con- from the original mixture. (N.U.J.B.)
tains the iron and sulphur in the proportion of 56 g of iron to 32 g
of sulphur, and no variation from this proportion is ever found.
Mixtures of iron and sulphur may, however, have any desired com-
position.
These differences between compounds and mixtures are summar-
ised below.

Mixtures
(a) The constituents can be sepa-
rated from one another by
physical methods.
(b) Mixtures may vary widely in
composition.
(c) Mixing is not usually accom-
panied by external effects such
as explosion, evolution of heat
or volume change (for gases).
((/) The properties of a mixture
are the sum of the properties
of the constituents of the mix-
ture.
Compounds
The constituent elements cannot
be separated by physical methods;
chemical reactions are necessary.
Compounds are absolutely fixed
in their compositions by weight.
Chemical combination is usually
accompanied by one or more of
these effects.
The properties of a compound are
peculiar to itself and are usually
quite different from those of its
constituent elements.

QUESTIONS
1. What are considered to be the main distinctions between a chemical

compound and a mixture? Explain why the liquid obtained by mixing

sodium chloride with water is not regarded as a chemical compound. (O.
andC.)
2. When a piece of sodium is placed in water it diminishes in size
gradually, and finally disappears. In what way is the disappearance of the
sodium different from the ordinary process of solution in water? Give

Chapter 2
Atomic Theory
WE have seen in the last chapter that there are about 100 kinds
of simple matter called elements, and that all other kinds of
matter have been formed by the chemical combination of two or more
of these elements. Thinkers have speculated for centuries in an en-
deavour to elucidate further the structure of matter, and, more
particularly, to shed light on the structure of the elements. The ancient
Greek thinker, Democritus (about 400 B.C.), began the speculations,
the Roman Lucretius (about 350 years later) took up the question,
and, following these two ancient philosophers, there has appeared
a succession of thinkers, European and Arabian, whose speculations
culminated at the beginning of the nineteenth century in the ideas of
an Englishman, John Dalton, of Manchester. His suggestions won
universal acceptance for themselves and lasting scientific fame for
their author.
Dalton
Dalton's life-time abounded in famous names and exciting hap-
—
penings the French Revolution, Austerlitz, Trafalgar, Nelson,
—
Napoleon, Wellington, Waterloo but the thoughts of this Quaker,
slowly maturing as he pursued an obscure and uneventful existence,
have proved more potent in their influence on human modes of living
in the succeeding century than all the wars and alarums of his day.
His Atomic Theory is the foundation of modern chemistry.
Dalton's love of precision and truth is illustrated by the following
story concerning him. Dalton had given a course of lectures, and at
the end a student came to him with the request for a certificate of
attendance. The great chemist looked up his records and found that
the student had missed one lecture during the course. Dalton refused
to sign the attendance certificate, but, after considering a few minutes,
he said, *If thou wilt come tomorrow I will go over the lecture thou
hast missed.' Having quietened his conscience in this manner over
the missed lecture, Dalton presumably signed the certificate.
12
ATOMIC THEORY 13
Ideas about atoms
You will have seen, from the work of the last chapter, that, if
ordinary powdered sulphur is mixed with water, it does not dissolve
and can be removed by filtration. That is, the sulphur particles are too
large to pass through the pores of the filter-paper. If, however, we
dissolve sulphur in carbon disulphide and filter the liquid, filtration
does not separate the sulphur. That is, the sulphur particles are now
small enough to pass through the pores of the filter-paper.
If sulphur is very finely ground and mixed with water, filtration
does not remove all the sulphur. Some is fine enough to remain
permanently mixed with the water in what is called a colloidal solution.
When this liquid is examined by the ultra-microscope, it can be seen
that sulphur particles are in rapid random motion, which continues
indefinitely at room temperature. This motion is now known to be
caused by collisions between the minute sulphur particles and par-
ticles (molecules) of water. The movement is shown by all colloidal
particles in water. It was first observed (1827) by the botanist, Brown,
for particles of pollen in water and is known as the Brownian
movement.
This idea that elements are capable of being split up into very tiny
particleswas first evolved by Greek and Roman thinkers from
another angle. They said that if we were to take a piece of, say, gold
and cut it up into small pieces, and cut those pieces into smaller
pieces, and those pieces into small pieces, and so on, a time would
ultimately come when the dividing process would have to stop. The
tiny particles of gold which we had then obtained would be in-
capable of being divided any further; they would be the smallest
possible particles of gold which could ever be obtained. The Greeks
gave them the name 'atoms'. As a temporary, though incomplete,
definition of an atom we may say that it is the smallest, indivisible
particle of an element. If the Greeks had been Englishmen they
might have called these particles 'indivisibles', for the word 'atom'
meant to a Greek what 'indivisible' means to an Englishman. We
still call them 'atoms' today.
Hypothesis and theory
The idea that elements are made up of atoms is called the atomic
theory. This word 'theory' does not often mean very much to a
beginner in Chemistry, so let us be quite clear about it. A scientific
theory is a scientific idea which was thought of by somebody,
suggested by him in a scientific book or journal, and accepted by
other scientists after due consideration. 'So-and-so's theory' means
'So-and-so's accepted idea'. The process of getting an idea accepted
 14 A NEW CERTIFICATE CHEMISTRY dalton's atomic theory 15

may bea long one; there will be arguments, objections, improve- being combined with oxygen in water— but the same number will be
ments of the idea, but, if it finally wins acceptance by scientists there.
generally, it will be called a theory. When the idea is first put forward,
and is still in the 'argument-and-objection' stage, it is called a hypo- The atoms of a particular element are all exactly alike in every way
thesis; later, if generally accepted, a theory. and are different from the atoms of all other elements
The most important point is that this statement includes in it the
idea that all atoms of the same element are exactly alike in mass, but
DALTON'S ATOMIC THEORY
are different in mass from the atoms of any other element. The
Dalton's Atomic Theory was first put forward in 1808. It soon theory said that if we collected together, say, one thousand atoms of
gained general acceptance and then stood, virtually unchanged, for sulphur from all corners of the earth, every one of those atoms of
about a century. Discoveries made early in the twentieth century, sulphur would be exactly the same as every other. The same would
however, showed that the theory must be modified. For this reason, be true of any number of atoms of copper. But the mass of each
the Atomic Theory will first be considered in its original, nineteenth- sulphur atom would be different from the mass of each copper atom.
century form; the changes made in it will be mentioned later, in Be sure you understand the universality of this idea. Consider, say,
Chapter 9. oxygen. Oxygen occurs in hundreds of thousands of compounds
The Atomic Theory, we have seen, goes back to the Greeks, yet we water, sugar, litharge, blue vitriol, alcohol, oil of vitriol, starch, and
always speak today about Dalton's Atomic Theory. There is good so on. If we were to collect one oxygen atom from each of these
reason for this. The reason is that, while the Greeks put forward the hundreds of thousands of compounds, every one of those oxygen
idea that atoms exist, they did no more. They left the idea vague and atoms would, said the Atomic Theory, be absolutely and completely
untested. Dalton changed this vague imagining into a set of concrete alike.
suggestions about atoms which could be tested by experiment. This It is clear that we could not test the theory in this way because the
change from vagueness to precision and experimental test justifies atoms are so small that we could not examine them or weigh them
his claim to the theory. Below are given the ideas which together even if we could separate them.
make up the Atomic Theory of Dalton (1808).
Idea on size of atoms
The Atomic Theory states: It is difficult to have any conception of the size of atoms. The
1. Matter is made up of small, indivisible particles called atoms. following diagram may help you to understand how small an atom
2. Atoms are indestructible and they cannot be created. really is.

3. The atoms of a particular element are all exactly alike in every

One gram of hydrogen liberated here and
way and are different from the atoms of all other elements. allowed to diffuse uniformly over the sur-
4. Chemical combination takes place between small whole num- face of the earth.
bers of atoms.

These ideas are so important that we shall discuss all except the
first more fully. This column of air (1
cm* CTOSS-section), any-
where on the surface of
Atoms are indestructible and cannot be created the earth, would contain
over 100,000 of those
The important aspect of this idea is that, by chemical action, it is hydrogen atoms. (It is
possible to alter only the state of combination of a number of atoms, assumed they are allowed
not to reduce their number or add to it. If we start a chemical to diffuse freely.)

reaction with, say, a thousand million atoms of hydrogen, then we

Fig. I.
shall finish that reaction with exactly a thousand million, neither
Idea on size of atoms.
more nor less. They may have altered their state of combination—
In other words, there are over 100,000 times more atoms in 1 g of hydrogen,
they may have become, for example, free hydrogen gas instead of
than square centimetres on the whole of the surface of the earth.
 16 A NBW CERTIFICATE CHEMISTRY
Chemical combination takes place between small whole numbers of
atoms
It follows from the supposition that atoms are indivisible that they
must combine in whole numbers. Dalton made the additional as-
sertion that these whole numbers are small. By this he meant that
atoms commonly combine in such numbers as 3 atoms of one
element with 1 atom of another, or 2 atoms of one element with 5
atoms of another, or 1 atom of one element with 1 atom of another.
Cases such as 67 atoms of one element combining with 125 atoms of
another, or 322 atoms of one element with 27 atoms of another, were
unknown. The numbers of atoms combining together are almost
always small, though, of course, in any one laboratory experiment
there will be millions of exactly similar combinations taking place.
We must now emphasise the fact that what has been
stated above is a set of ideas. In science, ideas are treated
with scant respect unless they can be backed up by experi-
mental results. None of the statements made above can be
tested by direct observation. We cannot line up a thousand
oxygen atoms and inspect them to see if they are all alike,
or count the number of hydrogen atoms which combine with
one atom of oxygen to see if the number is small. We must
deduce, from the Atomic Theory, some results which ought
to follow from it, and which can be put to experimental
test.
To find an experimental test of the Atomic Theory's assertion that
atoms are indestructible and cannot be created
If both these statements are true, it follows that the total number of
atoms present at the end of a chemical reaction must be the same as
the number present at the beginning of it, though they will be
differently combined. That is, the total mass of the products of a
chemical action should be the same as the total mass of the starting
materials. Experiment shows this to be true and the situation is
expressed in the Law of Conservation of Matter. Experiments suit-
able for illustrating it are given on p. 24, where the Law is formally
stated.
To find an experimental test of the Atomic Theory's assertion that all
atoms of the same element are exactly alike but different from atoms
of other elements
It isobvious from their different properties that atoms of different
elements differ from one another.
If atoms of the same element are all identical, it follows that all
SYMBOLS 17
pure samples of the same chemical compound must be identical in
composition by mass, however they are prepared. For example,
samples of black copper oxide, containing one atom of copper and
one atom of oxygen in each molecule, should have the same com-
position by mass, irrespective of the sources of copper and oxygen.
This can be tested by preparing copper oxide in several different ways
and analysing the various samples. Accurate experiment shows this
identityof composition in all the samples. The facts are stated in the
Law of Constant Composition (or Definite Proportions); suitable
experiments illustrating it are described on p. 26.
To find an experimental test of the Atomic Theory's assertion that
atoms combine in small whole numbers
If atoms combine in small whole numbers, the compounds formed
from elements with atoms A and B must be of the form: A,B„
AjB 2 A 2 B„ A a B 3 and so on. From this it follows that the mass A
, ,
of one element may combine with the masses B, 2B, £B, l^B, etc.
of the other element. But the mass A is a constant mass, because
all atoms of a given element are identical. Similarly, the mass B is a
constant mass. That is, the masses of B which combine with a
constant mass of A in their various compounds should be in the
ratio of 1 2 1 /2 3/2, which (multiplied by 2) is the ratio 2:4:1:3
: : :
This is a ratio of small whole numbers. That is, if the atomic theory
is true, the different masses of element B which combine with a fixed
mass of element A are in a simple whole-number ratio. Experiment
shows that these deductions are correct. The Law of Multiple Pro-
portions expresses the general situation and is stated, with experi-
mental illustrations, on p. 28.
Another law, the Law of Reciprocal Proportions, can also be
shown to follow from the portions of the Atomic Theory we are
considering. This is dealt with on p. 30.
We have now obtained, from the Atomic Theory, certain con-
clusions which can be made the subject of experimental test. It is the
magnificent achievement of Dalton to have been the first to state the
Atomic Theory, deduce from it these conclusions suitable for ex-
perimental check, and show that the experimental results support the
Theory. It is a piece of work which stamps Dalton as a scientific
genius of a very high order.
SYMBOLS
Having reached the conclu sion that elements are made up of atoms
needed some means of denoting atoms. Dalton invented a
scientists
system, which is now purely of historical interest and is dealt with
18 A NBW CERTIFICATE CHEMISTRY
briefly on p. 22. The modern simple system of representing atoms
was suggested by Berzelius, and consists generally of using the initial
letter of the name of the element to stand for one atom of it, e.g., one
atom of hydrogen is denoted by H, one atom of oxygen by O, one
atom of nitrogen by N. This rule cannot be universally applied
because 100 elements have to share 26 letters. The difficulty has been
readily overcome by using, for some of the elements, a symbol con-
sisting of the initial letter, as a printed capital, together with one
small letter from its name; for example, one atom of each of the
elements carbon, chlorine, cerium, calcium and cjesium is denoted
by the symbol C, CI, Ce, Ca and Cs. In the case of the metals, the
Latin names have sometimes been used as the source of the symbol
for example,

METAL LATIN NAME SYMBOL

copper cuprum Cu
iron ferrum Fe
lead plumbum Pb
silver argentum Ag
gold aurum Au
mercury hydrargyrum Hg
sodium (natrium) Na
potassium (kalium) K

These last two metals were unknown to the Romans, but a kind of
pseudo-Latin name has been bestowed upon each, and from this its
symbol is taken. A list of the symbols of the known elements is given
on p. 535.
Definition. The symbol of an element consists of one or more letters
which denote one atom of the element.
It is very important to keep it clearly in mind that the symbol of
an element does stand for a perfectly definite amount of it, and that
amount is one atom.

Molecules
Wehave seen that the smallest possible particle of an element is «
called an atom. It is obvious that the smallest possible particle of a
compound must contain at least two atoms because a compound must
contain at least two elements and cannot contain less than one atom
of each. To the smallest possible particle of a compound is given the
name 'molecule'.
The word molecule has, however, a wider meaning than this. We
have seen that the smallest possible particle of an element is called
 SYMBOLS 19

one atom of it, but it does not follow, necessarily, that single atoms
are the only particles normally existing in a mass of an element.
Actually most elements usually exist as a mass of more complex
particles, consisting of a number of atoms associated together and
moving as a To
more complex particle is given
single particle. this
the name 'molecule'. The between the atom and the mole-
distinction
cule of an clement is that the atom is the smallest particle of it which
can ever be obtained, and is the unit which is concerned in chemical
reactions, while the molecule is the smallest particle of the element
which is normally capable of a separate existence.
Try to get this distinction quite clear; the atom is the
smallest particle which can participate in chemical reactions
while the molecule is the smallest particle which can
normally exist when the element is not concerned in
chemical reaction.

Definitions. The atom is the smallest, indivisible particle of an element

which can take part in chemical change.
The molecule of an element or compound is the smallest particle of it
which can normally exist separately.
Actually, most of the elementary gases consist of molecules each
containing two atoms. The molecules of hydrogen, oxygen, nitrogen
and chlorine are all of this type; a proof of this statement cannot be
given until we have dealt with the Molecular Theory more fully, but
it will be found, applied to hydrogen, on p. 99. This state of com-

bination of the atoms is indicated by writing the molecules of these

gases as H
2 , O,, N» and Cl«, meaning a single unit consisting of two
atoms of each of the gases. (2H or 2CI would mean two separate
atoms of each of these gases, a condition in which they do not
normally exist.) The number of atoms in a molecule of an element is
called its atomicity.
Definition. The atomicity of an element is the number of atoms in one
molecule of it.

* SS83®cg>
<b 8
*!> <&89
Molecules of hydrogen, Molecules of ozone, Molecules of phos-
diatomic, H, Iriaiomic, phorus (in certain sol-
: ,

vents), polyatomic, P«
Fig. 2.

A molecule containing one atom is said to be monatomic,

e.g., He, helium.

-
i

- *Q
20 A NEW CERTIFICATE CHEMISTRY FORMULA AND EQUATIONS 21

A molecule containing two atoms is said to be diatomic, formula of copper oxide, water, sulphuric acid and calcium car-
bonate.
e.g., , N
H 2 2 , 2 , Cl 2 .

A molecule containing three atoms is said to be triatomic, When a group of symbols is common to a class of compounds, it is
frequently written as a bracketed group in their formula;, together
e.g., 3 ozone.
,

A molecule containing more than three atoms is said to be with a number to indicate the number of groups present. For example,
polyatomic, e.g., P 4 phosphorus, S„ sulphur. all from nitric acid,
metallic nitrates arc derived s , and they all HNO
contain the nitrate group or radical, NO
s , in their formula;. When
formula of nitrates are written, this group is preserved intact, and,
FORMUL/E AND EQUATIONS if two or more are needed, the number is indicated by enclosing

method of
the N0 3 group in number needed below
a bracket and writing the
From Berzelius' system of symbols is derived a simple
and to the right. This
arrangement is convenient because it em-
denoting molecules of a compound or element
phasises the relation of the nitrates to nitric acid. For example,
Anticipating a little, we have already seen that a molecule of an
Ca(N0 3) 2 means the same as CaN 2 O , because the 2 multiplies
element is denoted by writing the symbol of the element and, to the
everything inside the bracket, but Ca(NO s ) 2 indicates the relation
right and below it, a number expressing the number of atoms in the
of calcium nitrate to nitric acid, HN0
3 , more clearly than does
molecule; for example,
CaN 2 8 Similarly the formula of aluminium nitrate is written
.

H of hydrogen containing two A1(N0 3) 3 rather than A1N 3 0„.

2 denotes one molecule
atoms. The sulphate radical, S0 4 which is common to sulphuric acid,
,

P 4 denotes one molecule of phosphorus containing four HjS0 and 4, similarly treated. Thus the formula of
to all sulphates, is

atoms.
aluminium sulphate, written as AI 2 (S0 4) 3 indicates the derivation ,

of this compound from sulphuric acid, H 2 S0 4 more clearly than if

S 8 denotes one molecule of sulphur containing eight ,

written as A1 2 S 3 0, 2 The hydroxyl group, OH, is also preserved in

.
atoms.
formulae to emphasise the relation of hydroxides to water, H.OH,
The same device adopted in representing the molecules of com-
is which is regarded as hydrogen hydroxide. Thus the formula of ferric
pounds, though here, of course, at least two symbols must appear hydroxide is writtenFe(OH) 3 not Fe0 3 H 3
, .

because at least two elements must be present. Again, the small If it is necessary to indicate a number of molecules of a com-
figure, to the right of a symbol and below it, expresses the number of pound, this is done by writing the appropriate number before the
atoms of the element present, the figure 1 being omitted. A few formula of the compound; for example,
examples will make the idea clear.
2H 2 S0 4 means two molecules of sulphuric acid.
CuO denotes one molecule of copper oxide containing 8HN0 3 means eight molecules of nitric acid.
one atom of copper and one atom of oxygen. 4HC1 means four molecules of hydrochloric acid.
H 2
denotes one molecule of water containing two atoms 10H 2 O means ten molecules of water.
of hydrogen and one atom of oxygen.
It is important to notice carefully that the figure in front of the
H 2 S0 4 denotes one molecule of sulphuric acid containing
formula multiplies the whole of it. 2H 2 S0 4 for example, denotes two
two atoms of hydrogen, one atom of sulphur and four ,

molecules of sulphuric acid each containing two atoms of hydrogen,

atoms of oxygen.
one atom of sulphur and four atoms of oxygen, or four atoms of
CaC0 3 denotes one molecule of chalk (calcium carbon-
hydrogen, two atoms of sulphur and eight atoms of oxygen in all.
ate) containing one atom of calcium, one atom of carbon
and three atoms of oxygen. It is a common
mistake of beginners to think that the
figure multiplies only the symbol which immediately follows
The close proximity of the symbols denotes that the elements are it, for example, that in 2H S0
numbers 4 the 2 multiplies only the H,
in chemical combination. The collection of symbols and
2
and not the S0 4 . This is quite wrong. The 2 multiplies the
which together denote one molecule of a compound is called its whole of the formula HgSOj.
formula. Thus, CuO, aO, H H
2 S0 4 and CaC0 3 are
respectively the
22 A NEW CERTIFICATE CHEMISTRY questions 23

Notice that the formula of a compound denotes the perfectly Take another simple chemical equation.
definite amount of one molecule of it. Zn + H,S0 4 ->- ZnS0 4 + H 2

Dalton's system of symbols This means: 'one atom of zinc reacts with one molecule of sulphuric
acid producing one molecule of zinc sulphate and one molecule of
Dalton invented a number of symbols for the atoms of elements, a
hydrogen'.
few of which are:
Again, the formula of potassium chlorate being KCI0 3 and
, of
potassium chloride KC1, the equation
Hydrogen Oxygen Nitrogen Sulphur Carbon
2KC10 3 -> 2KC1 + 30
o o ©
8

means: 'two molecules of potassium chlorate decompose producing

Fig. 3. two molecules of potassium chloride and three molecules of oxygen'.
It is important to notice that there must be the same number of
He then indicated the formulae of compounds by combining the each kind of atom on the right of a chemical equation as on the left.
necessary numbers of these symbols, writing each one separately. Otherwise the equation would imply that atoms had been created or
Using modern knowledge of these compounds, his formula; would destroyed, which is impossible. This process of equalisation is called
be: 'balancing' (see p. 58).

Water Methane Sulphuric acid Ammonia

QUESTIONS
OCO
H.O
#
CH 4
$88
H,SO,
<$D
NH,
1. State
CuSO,.5H,0
the formula
the meaning of the following formula; a : KNO
(nitre),
(blue vitriol), PbCl s NajCO s .10H.O (washing soda), e.g.,
2H
,

(water) means that one molecule of water contains two

Fig. 4. atoms of hydrogen and one atom of oxygen.
2. How many atoms of the various elements arc indicated by the
This very laborious system is quite unsuited to the representation following formulas:
of complex molecules. Think, for example, of the task of represent- 2H s O, 5HCI, 7HN03 20PbSO IICu(NOI)1 ?
, 4,
ing on this system the formula of cane sugar, C 12 H 22 0,,. It would 3. Explain why
the terms 'atom* and 'molecule' can both be correctly
entail the drawing of 12 separate symbols for carbon, 22 for hydrogen applied to particles of an clement, but only one of them to particles of a
and 1 1 for oxygen, and the result would be an unwieldy and confusing compound.
jumble of 45 separate signs. The system was soon abandoned for that 4. What do you understand by the term 'atomicity'? What is the
of Berzelius.
atomicity usually assigned to the elements helium, chlorine, ozone,
phosphorus?
5. Why is the formula for lead nitrate written Pb(N03 ) a ? (It could also

EQUATIONS be written PbN,0«.) Give three similar examples.

6. Using the Atomic Theory as your illustration, show the importance of
It is now possible for us to represent chemical reactions by means the balance in determining the truth of a proposed theory.
of statements involving only formula; and symbols. 7. State briefly Dalton's Atomic Theory. Explain why the theory is
For example, if we wish to represent the fact that one molecule of named after him in spite of the fact that he was not the first to bring forward
the idea that matter consists of atoms.
copper oxide reacts with one molecule of sulphuric acid, producing
8. State the Law of Multiple Proportions and show how it is explained
one molecule of copper sulphate and one molecule of water, we can
by the Atomic Theory.
do so in the form: An element X forms two oxides containing 77.47 and 69.62 per cent of
CuO + H a S0 4 -> CuS0 4 + H 2 X respectively. If the first oxide has the formula XO, what is the formula
of the second oxide? (C.)
This kind of statement is called 'a chemical equation'.
The + sign on the left of the equation means 'reacts with', but on
the right it means simply 'and*, while the arrow means 'producing'.
 LAWS OF COMBINATION BY WEIGHT 25

Other substances suitable for the above experiment are given in

Chapter 3
Laws of Combination by Weight
The Law of Conservation of Mass
the following equations, which illustrate the chemical changes:
BaCl 2 + H S0 ->BaS0
2 1 4 -2HC1
Pb(N0 3 ) 2 + 2NaCI -»- PbCl a 2NaN0 3
There are many other examples.
These experiments are concerned with solutions. This is merely a
matter of experimental convenience. It is difficult to weigh gases,
(experimental) and solids are unsuitable because they do not generally undergo rapid
and complete reactions. The same experimental results are obtained,
however, when solids and gases are involved.
It must be noted, however, that a law of the kind we are dis-
cussing here is valid only within the limits of experimental error in-

THE Lawthatof matter

Conservation of Mass (or Indestructibility of Matter) volved. A
very accurate set of experiments carried out by Landolt
states neither created nor destroyed
is in the course about 1906 showed that the Law of Conservation of Mass is valid
of chemical action. (for the cases investigated) to about one part in ten million. For
Let us illustrate this by an experiment. most purposes, errors of this order are negligible. It should be noted
Into a conical flask put some silver nitrate solution and lower into also that, according to modern ideas, emission of energy during
it carefully by means of a thread a small test-tube full of hydro- chemical change involves loss of mass. The relation is expressed in
chloric acid. Insert the stopper (Fig. 5). Einstein's equation, E =
mc-, where E is the energy, the mass and m
Place the flask on the pan of the balance c the velocity of light (in appropriate units). In ordinary chemical
and weigh it. changes, the accompanying energy changes are so small that their
influence on mass cannot be detected by any weighing apparatus in
Note that you have just weighed
(besides those portions of the
common use. Nevertheless, the true conservation is one of mass-and-
energy together.
Cone. apparatus which are unchanged
Hydrochloric throughout) some water and silver Apparent destruction of coal
'
acid
nitrateand hydrogen chloride.
Silver
The above experiment may not seem conclusive to you because in
Allow the two liquids to mix by tilting it there seems little possibility of loss. If you consider the burning of
Nitrate.
'solution the flask a little, and you will observe a coal, where only a small ash is left, it seems much more likely that the
white precipitate of silver chloride whilst matter of the coal has been destroyed. The only real difference is that
nitric acid will be formed in solution. some of the reactants and products are invisible gases. Actually there
Fig. 5.
AgN0 3 + HC1 ->- AgCl + HN0 3 is no loss of matter at all. If we could weigh all the oxygen which
Experiment to illustrate
the Law of Conservation Replace the flask on the pan of the balance
of Mass. Small amount
and weigh again. You will find the weight
Invisible Invisible of soot, ash
is exactly the same as before. Invisible Visible water- carbon and other
oxygen coal vapour dioxide products
This time you were weighing (besides those portions of
00** 8>8> <£> .-.••*
the apparatus which are unchanged throughout) some water
and silver chloride and hydrogen nitrate (or nitric acid). 00 #+(coal} 8>8>«P + <V o> +
>

Hence, although substances may undergo chemical changes, the

total mass of the products of the reaction is exactly equal to the Weight of this = Weight of this
matter matter
total mass of the reacting substances.
24 Fig. 6.
26 A NEW CERTIFICATE CHEMISTRY THE LAW OF DEFINITE PROPORTIONS 27
burns the coal, and all the ash, soot, water-vapour and carbon dioxide poses, turning from green to black, and carbon dioxide is given off.
into which the coal is changed by the burning, we should again find —
(Test a drop of lime-water on the end of a glass rod is turned milky.
that the total mass of the materials before the reaction was the same The milkiness is caused by a precipitate of chalk.) Black copper(II)
as the total mass of the total products after it (Fig. 6). oxide is left. After heating it for some time, put the oxide into a
desiccator to keep it dry.

The Law of Definite Proportions CuC0 3 — CuO + C0 2

>-

(or Constant Composition)

Analysis of the samples of copper(TI) oxide by converting them to
The Law of Definite Proportions states All pure samples of the
: copper by heating in coal-gas.
same chemical compound contain the same elements combined in the
Weigh three clean, dry porcelain boats. Put into the boats 1-1$
same proportions by mass.
grams of the three samples of copper(II) oxide. Weigh all the boats
The illustration of this law entails the performance of several again. Put them into a hard glass tube and connect up the apparatus
experiments.
Principle of the Experiment. Copper(II) oxide (i.e., cupric oxide)
is prepared by several different methods and the samples are analysed
by reduction in a stream of hydrogen, or coal-gas, and shown to
contain copper and oxygen in the same proportions. Coa/oas

Preparation of the samples of copper oxide (copper(II) oxide)

Sample A. Starting from Copper. Place a little clean, pure copper
foil ina large crucible in a fume-chamber and carefully add concen-
trated nitric acid a little at a time. Brown fumes of nitrogen dioxide
(poisonous) are seen and green copper(II) nitrate solution is formed.
Cu + 4HN0 3 - Cu(N0 3) 2 + 2H 2 + 2NO, Fig. 7.

Evaporate the solution to dryness, then heat the green solid copper(II) Reduction of three samples of copper(II) oxide by coal-gas.
nitrate until no more brown fumes of nitrogen dioxide are evolved.
The black solid left is the first sample of copper(II) oxide. Store it as shown in Fig. 7. The tube must slope so that the end C is the
in a desiccator to keep it dry. lower.
Turn on and light it at the jet D. Then heat each boat
the coal-gas
2Cu(N0 3 ). -»• 2CuO + 4N0 2 -f 2
in turn. All the samples of the oxide will glow and leave reddish-
Sample B. Starting from Copper(II) Sulphate. Put some copper(H) brown copper. The water formed by the combination of the oxygen
sulphate solution into a beaker and add excess of caustic soda solu- of the oxide with the hydrogen of the coal-gas condenses at C, where
tion. A blue gelatinous precipitate of copper(Il) hydroxide appears. the tube is cooler. The end C is lower than the end A to prevent this
Heat the beaker and its contents on a tripod and gauze by means of a water from running back on to the hot part of the tube, which might
Bunsen burner. The precipitate changes to black copper(II) oxide. be broken. When the action is complete, allow the tube to cool,
CuS0 4 + 2NaOH - Cu(OH) 2 + Na t S0 4 keeping the coal-gas stream passing so that air cannot enter and
Cu(OH) 2 -> CuO oxidise the copper again. When the boats are cool, weigh
+HO a
all the
three boats again. Work out the results as shown below.
Filter off the black solid, wash it several times with hot distilled
water, and allow it oven or on a porous plate.
to dry in a hot CuO +H ^ 2 Cu + H2
Transfer the oxide to a crucible and heat it with a burner to drive from
coal-gas
off the last traces of water. Store the oxide in a desiccator.
Sample C. Starting from Copper(If) Carbonate. Place a little Within the limits of experimental error, the percentages of copper
copper(II) carbonate in a dry crucible and warm it gently. It decom- (and hence of oxygen) in all three samples of copper oxide are the
28 A NEW CERTIFICATE CHEMISTRY THE LAW OF MULTIPLE PROPORTIONS 29

same. It is found that, however samples of a given compound are hydrogen and the masses of copper which combine separately with,
prepared, they always contain the same elements in the same pro- say, 100 grams of oxygen in the two compounds, are calculated from
portions by mass. the weighings.
Weigh two clean dry porcelain boats and weigh them again con-
Specimen Results taining samples of pure, dry, copper(I) oxide and copper(ll) oxide
respectively. Reduce the oxides to copper in a stream of dry hydro-
Sample A Sample B Sample C gen, or coal-gas, as described in the last experiment. The preceding
table is a list of weighings and a specimen analysis.
Weight of porcelain boat 3.01 g 2.50 g 2.70 g Hence the masses of copper which have separately combined
Weight of porcelain boat and copper
4.26 „ 3.65 „ 4.14,, (i.e., to form the two different oxides) with a fixed mass, 100 g, of
oxide
Weight of porcelain boat and copper 4.02 „ 3-42 „ 3.85 „ oxygen are in the ratio 2 1. The law could have been illustrated
:

Weight of copper 1.01 „ 0.92 „ 1.15,, mass of copper.

just as easily by fixing the
Weight of copper oxide 1.25,, 1.15,, 1.44,,
1.01 x 100 0.92 x 100 1.15 x 100 If desired, the results of the above experiment can be expressed in
Percentage of copper in copper oxide
1.25 1.15 1.44 the following way, given the atomic weights of oxygen and copper as
= 80.8 = 80.0 = 79.8 16 and 63.5 respectively. (For mole, see p. 39.)

In copper(I) oxide
32
0.32 g of oxygen combine with 2.53 g of copper, so -^—- moles of
The Law of Multiple Proportions 16
2 53
The Law of Multiple Proportions two elements A and B
states: If oxygen atoms combine with --— moles of copper atoms. That is,
combine together to form more than one compound, then the several 63.5
masses of A, which separately combine with a fixed mass of B, are in 0.02 moles of oxygen atoms combine with 0.04 moles of copper
a simple ratio. atoms, i.e., the ratio of moles is 1 : 2.

In copper(II) oxide
Coppcrfl) oxide Copper(Il) oxide 0.38
0.38 g of oxygen combine with 1.52 g of copper, so moles of
-f—
16
Weight of boat 6.90 g 7.30 g
Weight of boat and oxide 9.75 „ 9.20,, oxygen atoms combine with -^— moles of copper atoms. That is,
Weight of boat and copper 9.43,, 8.82,, 63.5
.•. Weight of copper 2.53 „ 152,, 0.024 moles of oxygen atoms combine with 0.024 moles of copper
Weight of oxygen 0.32,, 0.38 „
.'. 0.32 g oxygen .". 0.38 g oxygen atoms, i.e., this ratio of moles is 1 1. From this, the numbers of
:

iscombined with iscombined with moles of copper atoms which combine with one mole of oxygen
2.53 g copper 1.52 g copper
100 g oxygen are 100 g oxygen are
atoms in the two compounds are in a simple ratio to one another
combined with combined with (2 1). Since one mole of oxygen atoms is a fixed mass, this result
:

2.53 x 100 1.52 x 100 agrees with the Law of Multiple Proportions. Also, the figures for
gcoppcr BCOpper
0.32 0.38 mole ratios point to Cu 2 and CuO as the simplest formulae for
= 790g = 400g copper(I) oxide and copper{II) oxide respectively. They were formerly
known as cuprous oxide, Cu 2 0, the red oxide, and cupric oxide,
This ratio is 2 1 withii l limits of experimental
:

en or
CuO, the black oxide.

Analysis of mercurous and mercuric chlorides as an illustration of the

Principle of Experiment. Copper and oxygen form two oxides, Law of Multiple Proportions
cupric oxide (copper(II) oxide, CuO) and cuprous oxide (copper(I)
The accuracy of the experiment described above depends on the
oxide, Cu 2 0). Pure samples of these two are reduced in a current of purity of cuprous oxide, a material extremely difficult to obtain in a
 30 A NEW CERTIFICATE CHEMISTRY QUESTIONS 31
pure state.Mercurous and mercuric chlorides can both be obtained theory, the idea that atoms exist which can be neither created nor
i.e.,

in a high degree of purity (Analar quality is used), and the following
experiment may be performed as a class illustration of the law.
Weigh a boiling-tube, add two or three grams of mercurous chloride,
and weigh again. Add a teaspoonful of sodium hypophosphite (see
p. 458), half fill with water, immerse in a beaker of water, and warm.
Repeat using mercuric chloride, taking care to distinguish between
the two boiling-tubes. After about 20 minutes, globules of mercury
are seen in each tube. Wash the mercury by decantation several times
destroyed in chemical action. Once a scientific law has been definitely
established it will usually stand for any relevant time, being well grounded
in fact. A theory put forward to explain the law may, however, be replaced
from time to time as knowledge increases.
QUESTIONS
1 g of one oxide of X contained 0.5 g of X, and 4 g of another oxide
1

with water (pouring the water into a beaker so that if mercury is lost,
of X contained 1 .6 g of X. Show these weights to be in accordance with

the Law of Multiple Proportions.

it may be retrieved), then with methylated spirit, and finally
with 2. Three oxides of nitrogen contain 53.3%, 69.6% and 36.4% of oxygen
ether. (Care! Extinguish all flames in the vicinity.) Replace the tubes respectively. Show that the Law of Multiple Proportions is upheld.
in the warm water for a minute to remove traces of ether, dry the 3. Show that the following results obtained by the reduction of the two
oxides of a metal are in agreement with the Law of Multiple Proportions.
outside,and weigh. Calculate the separate masses of chlorine associ-
ated with, say, one gram of mercury in each of the two chlorides.
These masses will be in the ratio 1 2. :
1st Compound 2nd Compound
NaHjPO, + 2HgCl 2 + 2H O
a NaH 2 PO« + 4HC1 + 2Hg
Weight or boat 5.30 g 4.45 g
sodium sodium
acid
hypophospitc Weight of boat + oxide 13.85 „ 13.05 „
phosphate
(powerful reducing Weight of boat + metal 12.12,, 12.08 „
agent)

The Law of Reciprocal Proportions 4. 1.90 g of one oxide of copper gave 1.52 g of copper on reduction.
2.85 g of another oxide gave 2.53 g of copper on reduction. Show these
This is a fourth law which can be deduced from the Atomic results to be in accordance with the Law of Multiple Proportions.
Theory. It is expressed in the statement: 5. Two oxides of a metal contained respectively 7.41% and 3.85% of
oxygen. Show these facts agree with the Law of Multiple Proportions.
If an element A combines with several other elements,
B, C, D, the 6. The sulphides of a certain element contained 33.7% and 20.4% of
masses of B, C, D, which combine with a fixed mass
of A are the sulphur. these figures agree with the Law of Multiple Proportions?
Do
masses of B, C and D which combine with each other, State the Law of Multiple Proportions. Describe how you would
7.
or simple
multiples of those masses. attempt to verify this law experimentally, if you were given specimens of
litharge (PbO) and lead dioxide (Pb0 2 ). Name one other pair of substances
Like the Law of Multiple Proportions, this law which you could use to verify this law. (N.U.J.B.)
can be derived 8. A
metal forms two oxides. 1.000 g of each oxide contains 0.239 and
from Dalton's assumption that combination takes
place between 0.385 g of oxygen respectively. Determine the equivalent of the metal in
small whole numbers of atoms, all the atoms each oxide and show that these figures are in agreement with the Law of
of a particular clement
being identical. Multiple Proportions. (C.)
9. State the Law of Constant Composition (that is, Definite Proportions).
Relation between scientific law and theory You are required to verify this law by using the black oxide of copper, and
for the purpose you are supplied with specimens of copper nitrate and
A scientific law
is simply a generalised
example
statement or observed facts. For copper carbonate. State clearly (a) how you would prepare specimens of
in ail cases examined, it has been found that the
total mass of copper oxide; (h) how you would use them to verify the law. (N.U.J.B.)
the products of a chemical action is equal
to the total mass of the original 10. State the Law of Definite Proportions. Describe fully the experi-
reagents. This result is assumed to apply
to <7//such cases and is generalised ments you would carry out in the laboratory in order to prove the truth of
as th £., w
k? °l Conservation of Mass. A scientific law is subject to two the law in the case of one chemical compound. (D.)
possibilities of error; first, it is not
the operation of the law. There may be
possible to examine every last case of 1 A A
A metal, X, forms two oxides, and B. 3.000 g of and B contain
1

millions of them. Second, the law 0.720 g and 1.160 g of oxygen respectively. Calculate the masses of metal
can be accurate only to the limit of experimental
error. ingrams which combine with one gram-atom of oxygen in each case. What
IS an ldea
P ut forward to explain the existence of one or more
i,*™™' u
laws. In the above case, the law is explained by a part of
chemical law do these masses of metal illustrate? Explain briefly. If the
Dalton's atomic oxide B has the formula XO, what is the formula of oxide A? (O = 16.)
32 A NEW CERTIFICATE CHEMISTRY
12. Three samples. A, B and C, all known to be oxides of a metal, M,
gave, by reduction in hydrogen, the following figures: 1.60 g of Aleft
1.28 g of M; 1.44 g of B left 1.28 g of M; 1.00 g of C
left 0.80 g of M.
Calculate the masses of M
that combine with one gram-atom of oxygen
in each case. Explain briefly what two chemical Laws are illustrated by the
results? If oxide A
has the formula MO, what are the formula; of B and C?
(O = 16.)
When
Chapter 4
1 3. 2 g of a metal, M, were converted
heated in dry chlorine, 1 . 1

to 3.25 g of anhydrous chloride, A. When heated in dry hydrogen chloride,

1 .400 g of M
were converted to 3. 1 75 g of anhydrous chloride, B. Calculate
the masses of M
which combine with one gram-atom of chlorine in these
chlorides. What chemical Law do these figures illustrate? Explain briefly. If Atomic Weight
the formula of A is MC1 S , write formula: for B and for the corresponding
sulphate of M. (CI = 35.5.)
14. Two oxides, A and B, of a metal, M, contained 70.0% and 77.8%
respectively of the metal. Calculate the masses of M
that combine with Introduction of the chemical balance
one gram-atom of oxygen in A and B. What chemical Law do these
figures illustrate? If B corresponds to a chloride MCl a what is the formula
of the chloride corresponding to A? (O = 16.)
,
AS soon as the existence of atoms
desirable to try to obtain as much
was recognised,it was obviously

information as possible about

theatoms of different elements, and, more particularly, to show how
theirweights compared with one another. This was necessary to
enable quantitative experiments of various kinds to be made, to test
doubtful points about the Atomic Theory, and also to enable
chemists to make calculations of the quantities of materials involved
in their experiments. Indeed, until the work of chemists could be
made the subject of accurate weighings, and calculations could be
tested by experiment, little progress could be expected. This was
recognised more particularly by Black, a Scottish scientist working
in Glasgow, and his name will always be honoured among chemists
for his persistent and pioneer use of the chemical balance for checking
his ideas. He taught scientists the importance of obtaining definite
quantitative results instead of the vague qualitative statements with
which they had been satisfied. The question for chemists became not
only 'What happens?' but also 'What weight of each material is
involved when it happens?'

Chaos of 1820-1850
We must not hide from ourselves thefact that the project of finding
out howthe weights of different atoms compared with each other
proved extremely difficult to carry out. For about forty years after
the Atomic Theory was suggested by Dalton, Chemistry was in a state
of chaos. It is difficult for us now to read with understanding any
book on Chemistry written between about 1820 and 1850, because
chemists were simply groping about trying to solve the problem of
comparing the weights of atoms, and they were making little progress.
Let us try to understand where the difficulty lay and to follow the
stages by which full knowledge was finally achieved.
In the first place, we must understand that chemists were not
33
34 A NEW CERTIFICATE CHEMISTRY ATOMIC WEIGHT 35

attempting to obtain the weights of individual atoms. It was clearly hydrogen'; or 'Every atom of phosphorus is 31 times as heavy as any
recognised that atoms were very small indeed and that there was no atom of hydrogen'. All this is conveyed by -= 16, Na 23, P O 31. = =
hope whatever at that time of obtaining the actual weight of a single You do not yet know how these figures have been obtained; take
atom of any element. The question was, rather: 'How do the weights them for granted for the moment. It will be obvious that if the
of the atoms of different elements compare with one another ? Is, for weights of all atoms are compared with the weight of a hydrogen
example, a sodium atom heavier than an atom of oxygen, and, if so, atom in this way, the weights of all atoms are also compared with
how many times? Is a silver atom heavier than an atom of gold, and, each other. When we say, for example, that the atomic weight
of
if so, how many times?' Actually, we can today find the real weight oxygen 16 and that of sodium is 23, we also state that the sodium
is
in grams of a single atom of any element; we have accomplished what heavier than the oxygen atom in the proportion of 23 to 16.
atom is
the chemists of 1830 regarded as a vain aspiration, but the process The fact that we have chosen the weight of a hydrogen atom as our
has taken 100 years, and when you read that the weight of a hydrogen unit of atomic weight leads to the statement that
the atomic weight
atom is 0.000 000 000 000 000 000 000 0017 g, you will not be sur- of hydrogen is 1 (H — 1).
prised that science has consumed a great deal of time, and the patient It is most important to get this idea of comparing the weights of
efforts of many, to reach a stage at which such a minute quantity can
all other atoms with that of a
hydrogen atom firmly fixed in your
be reasonably accurately measured. mind. Consider it for a moment from another angle. A fairly com-
plicated set of chemical experiments and theoretical arguments has
Meaning of the term atomic weight
established the conclusion that the atomic weight of sulphur is
Returning to the simpler problem of comparing the weights of 32 (S =
32). In the long run, this simply means that if
we could
atoms, it became necessary first to fix some standard of weight with of sulphur one single atom of place it on a
separate out from a piece it,

which all the atoms could be compared. We were measuring potatoes sufficiently delicate see-saw and then, to the other side of the see-saw
in stones, jam in pounds, and masses of steel in tons. In what weight-
units could we express the weights of atoms? To compare weights 32 HYDROGEN
I SULPHUR weighs k much *j ATOMS(H-l)
of atoms by using grams would, in fact, have been far less sensible ATOM (S- 32)
than trying to express the weight of grains of sand in tons. Chemists
recognised this and decided to compare the weights of all other
atoms with the weight of a hydrogen atom.
A
The hydrogen atom was chosen because it is the lightest Fig. 8.
of all the atoms and would give numbers greater than
unity for the comparative weights of all the other heavier add, one at a time, some hydrogen atoms, the see-saw would just
atoms. Tilts more convenient than working in fractions or
is
balance when exactly 32 hydrogen atoms had been added (Fig. 8).
decimals, which the choice of any other atom as standard In actual practice, we cannot separate out the one single atom of
would necessitate.
sulphur and the single atoms of hydrogen in this way, but, if we
Definition. The atomic weight of an element is the number of times could, all the chemical experiments which have been required to find
one atom of the element is as heavy as one atom of hydrogen. 1 the result S =
32 would be unnecessary.
You must understand clearly what this most important character-
istic of an atom is. If you look in a 'Table of Atomic Weights', you
Molecular weight
will see some statement such as O =
16 or Na 23 or P =31. This = The weights of molecules of elements or compounds are also com-
is the chemist's shorthand way of saying 'The atomic weight of pared with the weight of a hydrogen atom.
oxygen is 16, of sodium 23, and of phosphorus 31'; or, more fully, Definition. The molecular weight of an element or compound is the
'Every atom of oxygen is 16 times as heavy as any atom of hydrogen'; number of times one molecule of it is as heavy as of ONE ATOM
or 'Every atom of sodium is 23 times as heavy as any atom of hydrogen. 1

1
For modernisation of this definition, sec pp. 37, 39. 1
For modernisation of this definition, see pp. 37, 39.

36 A NEW CERTIFICATE CHEMISTRY
Early method for determining atomic weights
Considerable confusion existed in the chemical world in the first
half of the nineteenth century because of the difficulty of distinguish-
ing between atomic weights of elements and their combining weights.
For example, if two elements, A and B, combined in equal numbers
of atoms to give a compound of simplest formula AB, then their
combining weights were also their atomic weights. If, however, the
compound formed was A 2 B, the combining weight of A (in relation
to the atomic weight of B) was twice its atomic weight.
These difficulties were eventually overcome by the evolution of a
system in which the combining weight (called the equivalent) of an
element was referred to one gram of hydrogen and its combining
power (or valency) was referred to one atom of hydrogen. This led
to the definitions which follow.
The gram equivalent weight of an element is that number
of grams of the element which combine with, or displace,
one gram of hydrogen.
The valency of an element is the number of hydrogen
atoms which combine with, or displace, one atom of the
element.
From these definitions, it can be shown that the following relation
exists for any element:
Equivalent x Valency = Atomic weight
In this relation, atomic weight is & fixed quantity. The valency of an
element may, however, vary while always retaining a whole-number
ATOMIC WEIGHT 37
atomic weights by something under 1%, making, for example,
H =
1.008 (instead of exactly 1). The scale then remained unchanged
until 1962 when (for reasons connected with the mass
spectrometer),
modified very (a change of only 37 parts per million) by
it was slightly
basing it on the carbon isotope, £Ci which was given the atomic
weight of exactly 12 units. The older methods of atomic weight
determination have now been substituted by mass spectrometry. A
brief account of the mass spectrometer is given below.
With the present 12 C-scale of atomic weight, the gram-equivalent
of an element must theoretically be related to 3 g of carbon, since the
valency of carbon is 4. For practical purposes, however, the cor-
responding weights of elements such as hydrogen, oxygen and chlor-
ine are much more important and a working definition of equivalent
the following:
is
The gram-equivalent weight of an element is the number
of grams of the element that combine with, or displace,
3 grams of carbon-12, 1.008 grams of hydrogen, 8.00 grams
of oxygen or 35.46 grams of chlorine.
Experimental work relating to two or three methods of determining
equivalents is given in Chapter 6, with some corresponding practice
calculations at the end of the Chapter.
Note on the equation: Equivalent X Valency = Atomic weight
Recently, there has been objection to the use, by text-books, of this
equation on the ground that it does not (superficially) apply correctly
to certain cases. In particular, it is objected that the apparent

value. It will be shown later that this can occur because combining equivalent of iron (21) in the oxide, Fe 3 4 , bears no simple (valency)
power relation to the atomic weight of iron (56). It is known, however, that
is essentially an electronic phenomenon and an atom may
vary use of electrons, and the number used for combining
its the reaction of this oxide with warm, concentrated hydrochloric acid
purposes, according to its environment (within certain limits). This produces a mixture of iron(II) and iron(III) chlorides.
means that an element may have more than one equivalent. For Fe 3 4 + 8HCI - FeCl 8 + 2FeCl 3 + 4H Os
example, iron may use two electrons per atom for valency purposes
It seems, therefore, that iron, in Fe 3 4 , is acting with valencies of 2
(and is then known as iron{II)) and its equivalent (28) is half its
and 3 in the same compound, as FeO.Fe2 3 .
i.e.,
atomic weight (56); or it may use, as iron(HF), three electrons per
As iron(ll) or ferrous iron, its equivalent is 28, and as iron(III)
atom and have an equivalent of 18.7, i.e., one-third of its atomic
or ferric iron, 18.7. Iron(II) is combined with one-quarter of the
weight.
oxygen in Fe 3 and contributes 7 units to the apparent equivalent;
4
Difficulties and uncertainties of this sort were gradually overcome Fe 3 and
iron(III) is combined with three-quarters of the oxygen in 4
in the second half of the nineteenth century, and, before 1900, the three-quarters of 18.7). That the equa-
contributes 14 units (i.e., is,
atomic weights of about 90 elements were known with substantial = At. wt, applies accurately to the behaviour of iron(II)
tion, E X V
accuracy. At this time, the atomic weight scale was still based on
and iron(III) separately and to their joint behaviour if correctly
=
H I, which (from the composition of water) leads to O 15.88. = apportioned. A similar case occurs in triplumbic tetroxide, Pb 3 4,
Early in the twentieth century, it was agreed that the scale should
which acts as PbO a.2PbO.
be modified slightly by basing it on O =
16.00, which raised all
38 A NEW CERTIFICATE CHEMISTRY MASS SPECTROMETER 39
Modern atomic weight measurement. Mass spectrometer atom can be calculated and the height of the peak indicates the
A direct mode of determination of atomic weights has been avail- intensity of the beam.
able since 1920 through the mass spectrometer introduced by Aston. Aston's work of 1920 was notable not so much for its measurement
It must be remembered, however, that, by that date, the atomic of atomic weights as for its confirmation of the existence of isotopes.
weights of about 90 elements were fairly accurately known, and, at For example, chlorine (chemical atomic weight 35.5) showed two
first, the results from Aston's work had to be checked against known kinds of atoms (isotopes) to be present in it by producing two mass
atomic weights previously obtained from chemical experimentation. spectrum lines at 35 and 37 with intensities in the proportion of
Since 1920, however, the mass spectrometer has been greatly im- about 3 : 1.
proved and it can now give reliable, very accurate results. To a large Notice that atomic weight itself has no units; it is simply a number
extent, it has rendered chemical determination of atomic weights which states the relative mass of the atom concerned on a scale which
2
superfluous. gives the standard atom, '„ C, a mass of 12. If, however, the gram unit
In principle, the mass spectrometer first produces positive ions of is attached to the atomic weight, the quantity of the element thus

the element under investigation by causing its atoms to lose electrons. indicated is called one gram-atom or one mole of atoms. A mole of
This may be done, for example, by very strong electrical heating of atoms of any element always contains the same number of atoms,
6.02 x 1023 This figure is the Avogadro Constant, often called the
.

Avogadro number; its derivation is given on p. 107. The volume

S, S2
occupied by a mole of atoms of an element may vary enormously,
P 3
e.g., a mole of hydrogen atoms (1.008 g) occupies 1 1 200 cm at s.t.p.,
F +
while a mole of platinum atoms (195 g) occupies only 9.1 cm 3 in the

3>
ion
M
A same conditions.

source
Flo. 9.

Mass spectrometer.

a trace of a salt of the element on a tungsten filament, or by subjecting

a sample of the element in gaseous form to electron bombardment.
For a univalent element, X,
X-vX+-f e~
The stream of ions, X + , is selected by slits, S x and S 2 into a narrow ,

beam which is deflected and dispersed by the electrical field between

metallic plates at F. An electromagnetic field, M, at right angles to
the field, F, then focuses the beam on to a photographic plate, P, so
that all particles of the same charge/mass ratio fall on to a line
resembling an optical spectrum line. This line is an image of the
selecting slits. The whole process occurs at very low pressure. By
adding oxygen, O=
16, to the element under test, early experi-
menters could supply known lines at masses 8, 16 and 32 (represent-
ing ions O s+ , + and + O
g ) and use these as measuring standards
for the lighter elements. Modern instruments can be made to record
a graph on a moving paper roll. The graph shows a peak correspond-
ing to each ion beam, from which the mass of the corresponding
 TEMPERATURE AND PRESSURE CHANGE 41

occupies so large a volume that its pressure has also been reduced
to iP and the piston will then stop (Fig. 10, II). This will happen
when the volume of the gas has doubled; that is, a halving of the
pressure causes the volume of the gas to be doubled. Similarly, it
Chapter 5 would be found that if the pressure on the piston was reduced to
^P, it would come to a stop when the volume of the gas had in-
creased to four times its original value.
Expressing the result generally, the pressure of a gas decreases in
The Behaviour of Gases under Temperature the same proportion as its volume increases.

From this, it is clear that if we multiply the varying

and Pressure Change
volumes of a given mass of gas by the corresponding pres-
sures, any decrease in the value of one of them will be
exactly counterbalanced by the increase in the value of the
The nature of gas pressure other, and the result will always be the same.

ANY
which
gas consists of a collection of molecules of a particular kind
are in a state of rapid motion. The fact that the molecules
Expressed mathematically, this may be stated in the form:

are in motion is evident from the fact that if a small quantity of an p xv x =p tvt
(temperature constant)
odorous gas, such as hydrogen sulphide, is liberated at any point in a where p, and p t arc two pressures and v 1 and v 2 the corresponding
laboratory the smell of the gas soon pervades the whole room. volumes of a given mass of gas.
If the gas is confined in a closed vessel, some of the moving mole- This result is known by the name of its discoverer as Boyle's Law.
cules strike the sides of the vessel and each impact exerts a small force Boyle's Law. The volume of a given mass of gas is inversely propor-
upon the side. The number of molecules of gas inside such a vessel tional 1 to its pressure, if the temperature remains constant.
willnormally be very large and, on the average, the same number of
molecules will strike a given area on the sides of the vessel each Temperature change
second, so producing a steady pressure. common knowledge that a rise of temperature causes objects
It is

to expand and a fall of temperature causes contraction. The rule

Relation between pressure and volume applies to gases, liquids and solids but the effect is much more marked
Now suppose that one of the sides of a cylindrical vessel is a smooth in the case of gases than in the case of the other two. Charles found
piston and that there a pressure, P, exerted on the piston just great that, if pressure is constant, the volume of a gas increases or decreases
enough
is

to resist the pressure of the gas,

(Fig. 10, 1).
of which the volume is V
The piston will remain still.
by
that
^ its volume at 0°C for every °C rise or fall of temperature;
of
we take 273 cm 3 of any gas at 0°C, its volume will rise or
is, if

cm 3 for every °C rise or fall of temperature. Thus, at — C,

C
Now suppose that the pressure on fall by 1

the volume will be 272 cm at -2°C, 271 cm at -3°C, 270 cm and

3 3 3
the piston is suddenly reduced to \P, ; ;

without temperature change. The gas so on. This leads to the absurdity that, if the temperature falls to
pressure is the greater and the piston —273°C, the volume of the gas will be cm 3 the gas will have—
will move up. As it does so the gas will vanished In actual practice, no substance can remain gaseous at such
!

fill the greater volume now available. The low temperatures; all become solids and the Law of Charles does not
molecules be more loosely packed
will then apply, but this temperature, at which the volume of a gas would
in this larger space and so fewer will theoretically be reduced to zero, gives us the lowest possible tem-
strike the sides of the vessel in a given perature that can ever be reached. It is called absolute zero.

Fia. 10.
time; that is, the pressure of the gas Atemperature scale is in use starting from this absolute zero as 0°,
falls as the piston slides upwards. A
Effect of decrease in pressure 1
'Inversely proportional' is the mathematical expression of the fact that as
on a given mass of gas. stage will be reached when the gas
the pressure increases the volume decreases in the same proportion.
40
42 A NEW CERTIFICATE CHEMISTRY TEMPERATURE AND PRESSURE CHANGE 43

and using Centigrade (Celsius) degrees. This is called the Kelvin (K) pressure. What volume will it occupy (still gaseous) at — 20°C and
Scale in honour of Lord Kelvin who first suggested it. Measurements 770 mm pressure?
on this scale are stated in units, K, and a general kelvin scale tem- 18°C = + 273) K = 291 K
(18
perature is represented by the capital letter symbol, T. Since absolute
-20°C = (-20 + 273) K = 253 K
zero is the same as — 273°C, it is clear that the kelvin scale starts
measuring temperature from a point 273°C lower than the starting PlV i _ Pt»
Tx "
Then
point of the Centigrade (Celsius) scale and, to convert centigrade T,
temperatures to kelvin temperatures, we must add 273°. Thus: 740 X 21 1 770 X vt

-253°C is the same as 20 K (-253 + 273) 291 253

0°C is the same as 273 K (0 + 273) vs = 740 x 211 x 253
env*
15°C is the same as 288 K (15 + 273) 770 291
Restating the Law of Charles using kelvin temperature, we find that At this stage, inspect your fraction to see if it agrees with what common
273 cm 3 of gas at 273 K (0°C) will become 274 cm 3 at 274 K (1°C), sense would lead you to expect,
275 cm 3 at 275 K (2°C), 276 cm 3 at 276 K (3*C) and so on; for failing Thus (a), the 21 1 of the numerator, is the original volume of the
temperatures, the volume of gas will be 272 cm 3 at 272 K., 271 cm 3 gas in cm 3 The pressure is changing from 740 to 770 mm; that is, an
.

at 271 K, 270 cm3 at 270 K. and so on. This gives us the rule (known increase of pressure. This should decrease the volume. The fraction
as Charles's Law) that the volume of a given mass of gas increases
in the same proportion as its kelvin temperature, if pressure is —-
740
is actually doing so and is therefore correct.
constant.
Charles's Law. The volume of a given mass of gas is directly propor- (b) The temperature is falling from 291 K to 253 K; that is, the
tional 1 to its kelvin (absolute) temperature if pressure is constant. From 253
this follows that if we divide the varying volumes of a given mass
it
volume of the gas should be decreasing. The fraction — — decreases
of gas by the corresponding kelvin temperatures, any increase in the
the volume as required and is, therefore, correct.
volume will be exactly cancelled by the increase in the temperature,
and the result will always be the same. This can be expressed in the Using logarithms, vt = 176 cm 3
form
Standard temperature and pressure
(pressure constant)
Since the volumes of gases change in such a marked manner with
changes of temperature and pressure, it is necessary to choose a suit-
where u, and v 2 are the volumes of the gas at kelvin temperatures
able value of each as standards to which gas volumes can be referred.
7", and T respectively.
t
Combining with the equation expressing Boyle's
this Law (p. 41),
The standards chosen are 0°C and 760 pressure and these are mm
known as standard temperature and pressure, usually contracted to
we obtain the expression:
s.t.p.

That is, s.t.p. indicates standard temperature and pressure or 0°C

(273 K) and 760 mm
pressure (1 atm). In the past, the alternative,
N.T.P. (normal temperature and pressure) was used, the values being
and, by the use of this, we can find the volume, v it that a given mass
the same.
of gas will occupy at any desired temperature and pressure (7"2 andp t)
from its volume, v t at a given temperature and pressure (7\ and/?^.
,
Example. A certain mass ofgas occupies 146 cm 3 at li"Cand 738 mm
pressure. Calculate its volume at s.t.p.
Example. A certain mass oj gas occupies 21 1 cm 3
at 18°C and 740 mm
1
18°C = 291 K s.t. = 273 K (0°C)
Directly proportional is the mathematical expression of the fact that the
volume increases in the same proportion as the kelvin temperature increases. s.p. » 760 mm
44 A NEW CERTIFICATE CHEMISTRY
Pl"l _ Pt«t
Tt " Tt
738 X 146 760 X v.
291 273
Chapter 6
738 X 14 6 x 273 (Inspect this fraction
vt = as described above)
760 > 291
= 133 cm 3

Experimental Work on Formulae,

Dalton's Law of Partial Pressures
Reactions and Equivalents
This law states that, in a mixture of gases which do not act chem-
ically together, each gas exerts a partial pressure which is the pressure
it would exert if it alone filled the containing vessel at the same tem-

perature and pressure. Then the total gas pressure is the sum of the THIS chapter deals with experimental work whichcompounds
can be used to
and
partial pressures of the constituent gases. determine some empirical (simplest) formula; of
This law applies most commonly to the case of a gas collected over the numbers of various atoms involved in some displacement re-
water. For example, suppose 100 cm3 of an insoluble gas are col- actions. Atomic weights of elements involved are assumed known
lected over water at a barometric pressure of 745 and at 15°C. mm and are quoted.
If it is saturated with water-vapour, the true pressure of the gas is
(745—13) mm, since the vapour pressure of wate rat 15°C is 13 mm.
Displacement of hydrogen by metal
Dry, at s.t.p., the gas would occupy 100 x
732
760
x
273
288
- cm
1 - — .

Many metals displace hydrogen from dilute acids. For experi-

mental purposes, magnesium is convenient because it reacts rapidly
with either dilute hydrochloric or dilute sulphuric acid at room tem-
QUESTIONS perature. The purpose of the present experiment is to determine
Calculate the volumes which will be occupied at the given final tem- (given Mg = 24 and H = 1 .008) what numbers of atoms of mag-

peratures and pressures by the gases whose initial volumes, temperatures

nesium and hydrogen displace one another in the reaction. Mag-
and pressures are given.
nesium is weighed normally on a chemical balance but hydrogen
(being the lightest known gas) is more conveniently measured by
volume and converted to weight from the fact that one dm (litre) of
3
Volume Initial T. & P. Final T. & P.
hydrogen at s.t.p. weighs 0.09 g.

<?> 273 cm' 0"C and 760 mm 14°C and 861 mm Experiment. Weigh a small watch-glass, then put on to it about
1638 cm' 0°C and 819 mm !5°Cand 864 mm 0.25 g of cleaned magnesium ribbon and weigh again. Obtain the
1 1000 cm' -23°Cand750mm 23°C and 800 mm weight of the metal by difference. Without the conical flask in posi-
W> 500 cm' l7°Cand870mm -48°C and 750 mm
K
(/)
1000 cm'
760 cm'
182°Cand722mm
27°C and 700 mm
s.t.p.
s.t.p.
tion (Fig. 11), fill the siphon tube with water by blowing gently into
the short tube attached to the aspirator. Close the clip and place the
The exam pies below need the use of logarithms delivery tube in the measuring cylinder. (This procedure is necessary
because at the end of the experiment the siphon tube will be filled
700 cm' 17°C and 740 mm
k s.t.p.
1

133 cm' :
I4°C and 745 mm 17°C and 750mm with water and, if it were left empty at the start, the volume of water
o) 55 cm' 1
14°C and 744 mm s.t.p. delivered would be too low.) Using a funnel (to keep acid away from
O) 574 cm' 1
s.t.p. I5'C and 735 mm 3
the upper sides) pour about 30 cm of dilute hydrochloric acid into
Qo 70 cm' 18°C and 745 mm
'

s.t.p.

tL
121 cm' 150°Cand780mm 120°C and 742 mm a conical flask, carefully place the weighed magnesium as shown and
(m) 534 cm' s.t.p. -15°Cand740mm connect the conical flask to the aspirator (supporting it suitably).
45
 :

46 A NEW CERTIFICATE CHEMISTRY EXPERIMENTS ON BLACK COPPER OXIDE 47

Siphon Lube, Open the If the apparatus
clip.
This is an almost exact ratio of 2 : 1 in moles, i.e., one atom of
full of water
is water will flow for a
airtight, magnesium has displaced two atoms of hydrogen from the acid. This
second or two, then stop. (If it corresponds to the equation
continues longer, a leak exists and
Magnesh must be remedied.) Shake the mag-
Mg + H S02 4
->• MgSO« +H 2

Dilute, nesium into the acid. When all the If desired, this experiment can be used to calculate the equivalent of
acid
metal has dissolved, allow time magnesium as below.
for the apparatus to cool. Then From the results:
adjust the levels of water in the 0.0217 g of hydrogen are equivalent to 0.26 g of magnesium
measuring cylinder and aspirator Therefore,
to equality (by raising or lowering 1.008
Fio. II. one of the two as required). This 1.008 g of hydrogen are equivalent to 0.26 X g of magnesium
0.0217
Displacement of hydrogen. gives atmospheric pressure in the
or 12.1 g. This (by definition, p. 37) is the gram-equivalent weight
aspirator. Read the volume of
water in the measuring cylinder, after closing the clip and removing of the metal.
the cylinder. This volume is also the volume of hydrogen liberated.
Room temperature and the barometer reading are required.
Experiments on the formula of black copper oxide
Specimen readings Black copper oxide contains only copper and oxygen. Evidence
Weight of magnesium — 0.260 g about its formula may be obtained either by analysing it by reduction
Volume of hydrogen = 252 cm 3
in hydrogen (with heat) or by synthesising it by oxidation of the pure
Room temperature = 10°C metal, both processes being quantitative.
Barometer reading = 752 mm (corrected for
vapour pressure of water) Method I. Reduction of the oxide

1. Reduce the volume of hydrogen to s.t.p. Black copper oxide has been made by the chemical union of copper
and oxygen. By the removal of oxygen in a stream of hydrogen the
.Wi 752 X 252 760 X v t
weights of copper and oxygen which were in combination can be
'
Ts 283 273 determined (Fig. 12).
752 x 252 x 273 _,. _ (Coal-gas can be used instead of hydrogen for this experiment. Its
From this, Vi ~- 283X760
=240 5cm3 -
use is not dangerous.)
The tube must slope downwards towards A, otherwise water con-
2. Find the weight in grams of this volume of hydrogen densed during the experiment might run back on to the heated part
1000 cm 3 of hydrogen at s.t.p. weigh 0.09 g and crack the tube.
so 1 cm3 of hydrogen at s.t.p. weighs 0.00009 g Weigh a porcelain boat and weigh again with some pure dry copper
and 240.5 cm of hydrogen
3
at s.t.p. weigh 0.00009 X 240.5 oxide in it. Place the boat inside a hard glass tube. Generate hydrogen
g
or 0.02165 g as in Fig. 12 and pass it through a calcium chloride tube to dry it.
Approximating slightly on the experimental results: 0.0217 g of Allow the hydrogen to pass over the oxide until, when collected in a
hydrogen are displaced by 0.260 g of magnesium. Assuming the test-tube as shown, it burns quietly on exposure to a flame. This shows
atomic weights of hydrogen and magnesium to be 1.008 and 24 that all the oxygen in the apparatus has been expelled. Then light the
respectively, the number of moles of hydrogen and magnesium
atoms hydrogen at the jet and warm the copper oxide. Soon a glow spreads
which replace one another are: through the oxide (an indication that chemical change is taking
place). A reddish-brown powder, copper, is left, and drops of water
and °™. or 0.0215 and 0.0.08 A.
collect at
1.008 24 *

Allow the copper to cool in a current of hydrogen so that air

48 A NEW CERTIFICATE CHEMISTRY EXPERIMENTS ON BLACK COPPER OXIDE 49

cannot enter and so convert the red metallic copper into the oxide oxide is CuO. This is copper(II) oxide in which the valency of the
again. metal is 2.
Weigh the boat and copper when cool. (The boat and contents If desired, the equivalent of copper in this oxide can be calculated
should, to ensure complete reaction, be heated to constant weight.) from the experimental results as below:
Note that the copper oxide has been reduced by the hydrogen to 0.26 g of oxygen are equivalent to 1.03 g of copper,
red metallic copper, whereas the hydrogen has been oxidised to water. 1 03 X 8 '

(See p. 162.) so 8 g of oxygen are equivalent to g of copper, or 31.7 g

0.26
CuO + H, -> Cu -f H,0 of copper.
copper hydrogen copper water This (by definition, p. 37) is the gram-equivalent weight of copper.
oxide If coal-gas is used for this experiment, all details are the same
except that the air can be swept out so quickly that there is no need
to test for its removal.
Cone. Hydrochloric
- Acid For class use, the following method is satisfactory:
Blow a small hole in a test-tube and weigh the test-tube. Weigh
again with some pure dry copper oxide in it. Push the rubber tube

CuO + H, ->• Cu + H.O

Clock-glass

ffOS Dilute Nitric

Zinc and acid
Water
Calcium. Chloride
to dry the
hydrogen

Fig. 12.

Reduction of copper oxide by heating in hydrogen.

it
Fig. 13. Fig. 14.

Specimen analysis from the Bunsen burner into the test-tube, pass coal-gas through it
and light it as shown in Fig. 13.
Weight of boat = 4.32 g
Conduct the experiment in a similar manner to that described in
Weight of boat h oxide = 5.61 g
the previous experiment and work out the result.
Weight of boat + copper = 5.35 g
.'. Weight of oxygen =
0.26 g Method 2. Oxidation method
.". Weight of copper =
1.03 g
Weigh a small evaporating dish and clock-glass (7.5 cm diameter is
0.26 g of oxygen has combined with 1.03 g of copper
suitable), and weigh again having added one or two small pieces of

Assuming the atomic weights of oxygen and copper to be 16 and copper (not more than half a gram). Remove the clock-glass, add
63.5 respectively, the number of moles of oxygen atoms and about 10 cm 3 of bench dilute nitric acid (approx. 4M), replace the
copper
atoms which combined together are: clock-glass, and heat gently on a tripod and gauze in a fume-chamber
(Fig. 14). There is a vigorous effervescence, brown fumes of nitrogen
and °' 016 ( a PProx -) in
dioxide are seen, and the copper finally dissolves, giving a blue solu-
~\6 63~5 °r both cases
tion of copper(ll) nitrate.
This means that, black copper oxide, copper and oxygen atoms
in 3Cu + 8HN0 3 -* 3Cu(N0 3) 3 -f- 2NO + 4H 2
combine together in equal numbers and the simplest formula of
the 2NO + O l -»-2NO,
 50 A NEW CERTIFICATE CHEMISTRY
Continue to heat the solution (increasing the size of the flame to
maintain a steady but not too vigorous evolution of vapour) until the
whole of the excess nitric acid has been driven off and the copper(H)
nitrate converted to black copper oxide.

2Cu(N0 3) a - 2CuO + 4NO s +O a

copper copper nitrogen oxygen
nitrate oxide dioxide
Heat the dish very strongly fora few minutes to decompose any
copper nitrate on the sides of the dish or on the clock-glass, allow to
cool (in a desiccator if possible) and weigh the dish and clock-glass.
Repeat the heating to constant weight. (The clock-glass minimises
loss of liquid by spurting but does not materially reduce
the rate of
evaporation.)

Specimen weighings
Weight of evaporating dish and clock-glass = 20.210 g
Weight of the above +
copper = 20.634 g
Weight of the above -f- copper oxide = 20.741 g
Weight of copper used = 0.424 g
Weight of oxygen combined = 0.107 g
From these figures, 0.107 g of oxygen combined with 0.424 g of
0.107
copper. Given that O= 16 and Cu = 63.5, moles of oxygen
16
0.424
atoms combine with -j—- moles of copper atoms. These are equal

numbers of atom moles at the value of 0.0067 approximately. That

is,the simplest formula of the black oxide is CuO and it is
copperiJI)
oxide in which the valency of copper is 2.
If desired, this experiment gives the equivalent of copper
in this
oxide, as below. From the results,
0.107 g of oxygen are equivalent to 0.424 g of copper,

°' 4 4 * 8
so, 8 g of oxygen are equivalent to -I of copper, or
q
31.7 g.
This (by definition, p. 37) is the gram-equivalent weight of the metal.

Experiment on the reaction between zinc and

copper(II) sulphate solution

Crush a quantity of copper(H) sulphate crystals (about

5 g) in a
mortar and dissolve them in water in a beaker, warming
to hasten
the solution. Weigh a small watch-glass, add a few
strips of pure
Plate 4. Welding
chain links in the
factory of Messrs QUESTIONS 51
Watson and Mac-
lean. zinc foil (weight about 1 g) and weigh again. The weight of the zinc

can be obtained by difference. Put the zinc into the copper(ll) sulphate
solution. Immediately the zinc becomes coated with a red film of
copper and. on stirring, the copper falls to the bottom of the beaker.
After a while the whole of the zinc will have disappeared and there
will be a layer of red metallic copper on the bottom of the beaker.
(More copper(II) sulphate crystals can be added if the colour indi-
cates that the solution is dilute.)

Filter off the copper and wash the small particles of copper adher-
ing to the beaker into the filter-paper by means of a jet of water from
a wash-bottle. Wash the copper several times with hot distilled water,
and finally two or three times with methylated spirit (care being
taken to extinguish any burners likely to set fire to the spirit). Allow
the copper to dry and weigh it, together with the filter-paper, a clean
filter-paper being placed on the right-hand pan of the balance and
the weights on top of the filter-paper.

Specimen calculation
Weight of zinc used = 0.920 g
Weight of copper displaced = 0.890 g
0.920
Given Zn = 65 and Cu = 63.5, moles of zinc atoms displaced
65

moles of copper atoms. That is, the number of moles of zinc

and copper atoms concerned is equal at 0.014 approximately. This is

in accordance with the equation:

Zn + CuS0 4 -»- ZnSO« + Cu

in which one atom of zinc replaces one atom of copper. (The reaction
is really ionic as:

Zn + Cu 2+ -> Zn a+ + Cu)

QUESTIONS
1. Sketch and label an apparatus suitable for heating an oxide of
copper in a current of dry hydrogen. State two precautions (with reasons
for them) which are necessary for the safe conduct of the experiment.
Describe what happens to the oxide of copper when heating begins. If
0.429 g of oxide were reduced to 0.381 g of copper in an experiment, which
oxide of copper (CuO or Cu s O) was used? (Cu = 63.5; O = 16.)
2. Sketch an apparatus suitable for measuring the volume of hydrogen
liberated by the action of a known weight of magnesium on excess of dilute
hydrochloric acid. Indicate the precautions and readings necessary to
obtain a reasonably accurate result. If0.200gof magnesium liberate 187 cm'
of hydrogen (dry) at s.t.p., calculate the ratio of magnesium used to

Right: The com

plcted link
 1

52 A NEW CERTIFICATE CHEMISTRY QUESTIONS 53

hydrogen liberated in terms of gram-atoms. (Mg =
1000 cm' of hydrogen at s.t.p. weigh 0.09 g.)
3. Ametal, X, precipitates copper quantitatively from copper sulphate
solution. In an experiment, 0.480 g of X
were found to produce 1 .270 g
of copper after purification. If the equation for the reaction is:
X+ CuSO, —*- XSO, + Cu
calculate the atomic weight of X. (Cu = 63.5.)
4. 0.480 g of clean magnesium ribbon was slowly burnt in air with no
appreciable loss of material. The cooled product was moistened with water
(to destroy any magnesium nitride) and the resulting material was strongly
heated to constant weight (0.800 g) of magnesium oxide. Given Mg = 24
and O= 16, calculate the gram-atom ratio in which the two elements
react and write the simplest formula of magnesium oxide.
5. 1 .800 g of aluminium was dissolved with heat in slight excess of dilute
hydrochloric acid. Aluminium hydroxide was precipitated by the addition
of slight excess of ammonia solution and, after filtration, washing, drying
and strongly heating to constant weight, 3.400 g of aluminium oxide
remained. If the atomic weights of aluminium and oxygen are 27 and 16
respectively, deduce from the above data the simplest formula of aluminium
oxide. (Use gram-atom ratios.)
6. When suitably heated in oxygen, leadcan produce a red compound
24; H= 1.008; weight of M = 27; = 16; 1000 cm 3 of oxygen weigh 1.44 g at s.t.p.;
O
saturated vapour pressure of water at 15°C is 13 mm.)
11. 0.360 g of metal, M, liberate from excess of dilute hydrochloric acid
366 cm 3 of hydrogen (over water) at 15°C and 750 mm pressure. If, also,
hydrogen and chlorine combine together in equal volumes at constant
temperature and pressure and the valencies of all three elements remain
constant, deduce (by reference to gram-atom quantities) the simplest
formula of the chloride of M. (Atomic weight of M is 24; CI 35.5;
1000 cm 3 of chlorine weigh 3.20 g at s.t.p.; saturated vapour pressure of
water is 13 mm at 15°C.)
12. 0.934 g of a sample of granulated zinc containing a small percentage
3
of non-reactive impurity yielded 356 cm of hydrogen (over water) at
740 mm pressure and 17°C by reaction with excess of dilute hydrochloric
acid. By converting these quantities to gram-atoms, show that, with respect
to zinc and hydrogen, these figures agree with the equation:
Zn + 2HCI -+ ZnCl, + H,
(allowing slight error for the impurity). Calculate the percentage of the
impurity in the zinc (to one significant figure). (Zn = 65; H = 1.008;
1000 cm 3 of hydrogen at s.t.p. weigh 0.09 g; saturated vapour pressure of
mm.)
water at 17°C is 14
13. Ametal has an equivalent weight of 12. Calculate the weight of
metal required to liberate from acid 525 cm' of hydrogen (dry) at 5°C 1

said to be Pb3 0«. (This red compound can be entirely reduced to lead at and 750 mm
pressure. (1 dm 3 or litre of hydrogen at s.t.p. weighs 0.09 g.)
red heat in a current of dry hydrogen.) Describe, in detail, an experiment
14. 0.162 g of a metal, X, were converted to 0.801 g of its chloride.
by which (using this reduction) you would test the accuracy of the quoted Calculate the equivalent of X. If the valency of X
is 3, what atomic
formula. Outline any required calculation. (Pb = 207; O = 16.)
is its

weight? (CI = 35.5.)

7. Two oxides of lead, A and B, were heated in dry hydrogen to reduce
them to metallic lead. In case A, 0.446 g of oxide left 0.414 g of lead; in
case B, 0.717 g of oxide left 0.621 g of lead. Show that these figures are in
accordance with the Law of Multiple Proportions and, given Pb = 207
and O = 16, calculate the simplest formula: of A and B.
8 0.108 g of a metal, M, of atomic weight 27, liberated 134 cm' of
15. The oxide of a certain metal is completely decomposed into its
elements by heat. Describe an experiment suitable to determine the volume
of oxygen given off from a known weight of the oxide (mentioning pre-
cautions needed for reasonable accuracy). If the volume of oxygen obtained
from 1 72 g of the oxide is 94 cm 3 at 2°C and 750
. 1 mm pressure, what is the
equivalent of the metal? (1 dm 3 or litre of oxygen at s.t.p. weighs .44 g.)
1

H
hydrogen (measured dry) from an acid, a X, at s.t.p. Make the calculations 16. 2 g of a metal yielded 844 cm 3 of dry hydrogen from dilute acid at
(in gram-atom terms) which are needed to determine the simplest
values
17°C and 765 mm pressure. Also, 4.20 g of the same metal were converted
for n and m
in the equation: to 6.00 g of its oxide. Calculate the two equivalents of the metal, explain
nM + twH.X —> M»Xm + mH, why they are different and use the results to illustrate the Law of Multiple
Proportions. (Sec Q. 13 for hydrogen data.)
(H = 1.008; 1000 cm 3 of hydrogen at s.t.p. weigh 0.09 g.)
9. 0.180 g of aluminium liberated, from dilute hydrochloric acid,

235 cm 3 of hydrogen, measured (dry) at 10°C and 750 mm pressure. If the

equation for this reaction is:

Al + xHCl -»• Aid, + lH *

deduce (from the data given) the value of x. (Al = 27; H = 1.008;
1000 cm 5 of hydrogen at s.t.p. weigh 0.09 g.)
108 g of a metal, M, liberates 147 cm of hydrogen
10
8 from a dilute
mineral acid, measured (over water) at 15°C and 745 mm
pressure. Given

also that hydrogen and oxygen combine in the

volume ratio of 2 :
respectively (at constant temperature and pressure),
deduce by reference
to gram-atom quantities the simplest
formula of the oxide of M, assuming
that the valencies of the elements concerned
remain constant. (Atomic
 CALCULATIONS INVOLVING WEIGHTS 55

first and then proceed as above. Thus: Calculate the molecular weight
of calcium nitrate, Ca(N0 3 ) 2 (Ca . = 40; N = 14; O= 16.)
Ca(NO,) 2
orCaN 2 0«
Chapter 7 40 + (2 x 14) + (6 x 16)
= 40 + 28 +
96
164 = =
molecular weight of calcium nitrate
Later, with practice, you will be able to carry out the removal of the
Calculations Involving Weights bracket mentally.
It is also possible to calculate the weight of each element present in
a given weight of compound from its formula. This information is

usually stated as the percentage composition of the compound.

WE have seen in Chapter 2 that every definite chemical reaction
can be represented by means of an equation. In Chapter 4, the To calculate the percentage by weight of each clement present in a
question of atomic weights was considered. In the present chapter compound from its formula
we shall combine the knowledge obtained in both and show how a Example: Calculate the percentage by weight of each element in
quantitative meaning can be assigned to an equation in terms of the calcium sulphate. CaSO A (Ca = 40; S = 32; O = 16.)
.

commonly used weight units— more particularly the scientific unit, First calculate the molecular weight of calcium sulphate.
the gram.
CaS0 4
To calculate the molecular weight of a compound from
40 + 32 + (4 X 16)
its molecular = 40 + 32 + 64
formula
= 136.
We have noted that the molecular formula of a compound indi- 40 of these 136 units of weight are calcium, that is, the fractional
cates the kind of atoms present in the molecule and their number;
weight of calcium in calcium sulphate is 40/136. Then the percentage
thus the formula H 2 S0 4 , for sulphuric acid, indicates that one mole-
cule of the acid contains 2 atoms of hydrogen, 1 atom of sulphur and weight is —x
40
136
100 or 29.4.
4 atoms of oxygen. The atomic weight of each of these elements is
known and can be obtained from tables. The molecular weight of Similarly the fractional weight of sulphur is —32— and the percentage
sulphuric acid can now be calculated by allowing the appropriate 136
number of weight units for each element present and adding to
obtain the total. (H = 1 ; S = 32; O = 16.)
is ~x
136
100 or 23.5.

Thus H, S 4
The percentage weight of the third element, oxygen, need not be
(2 X 1) + 32 + (4 X 16) calculated as it is given by the expression 100 — (% of calcium + %
= 2 + 32 + 64 of sulphur),
= 98 = molecular weight of sulphuric acid or 100 - (29.4 + 23.5)

Taking another example: Calculate the molecular weight of red

= 47.1
lead, PZ> 3 4. (Pb = 207; O = 16.)
These calculations can be set out compactly as below: Calculate

Pb 3
the percentage composition of calcium hydroxide, Ca (OH) (Ca
a 40; . =
4 O= 16; H= 1.)
(3 X 207) + (4 x 16)
Ca(OH),
= 621 + 64 or Ca0 H,
= 685 = molecular weight of red lead
+ (2 x 16) +
40
2

(2 X 1)
If the formula of the compound contains bracketed acid radicals, it
= 40 + 32 + 2
will be simpler and more accurate for you to remove the brackets = 74
54
56 A NEW CERTIFICATE CHEMISTRY CALCULATIONS FROM EQUATIONS 57

40 40 That the formula Na 2 C0 3

Calcium. Fractional weight — . Percentage weight — X 100
The
is,

calculation
is .

out compactly in the following example:

is set
74 74
= 54.1 Calculate the formula of a compound which has the composition:
32 32 magnesium 9.8%, sulphur 13%, oxygen 26%, water of crystallisation
Oxygen. Fractional weight — . Percentage weight — X 100
51.2%. (Mg - 24; S = 32; O = 16; H aO = 18.)
74
i* 74
/•

= 43.2 Magnesium Sulphur Oxygen Water

Hydrogen. Percentage weight = 100 — (54.1 + 43.2) = 2.7
It is also possible to calculate the formula of a compound from its % by weight 9.8 13 26 51.2
composition by weight. 26
Ratio of atoms or
molecules g- 0-408 g- 0.406 16
- lM
= fil I
5
-!^
18
= 284
*•**

To calculate the simplest formula of a compound from its composition Divide by smallest (or 0.408 0.406 1.63 2.84
by weight smallest difference) 0.406 0.406 0.406 0.406

This calculation is illustrated by the following worked example. 1 1 4 7

Calculate the formula of a compound which has the following per-

centage composition: sodium 43.4, carbon 11.3, oxygen 45.3.
.'. the formula is MgS0 4 .7H s O
(Na = 23;C= 12; O = 16.) Empirical and Molecular Formula; are discussed on p. 107.
The fact that the atomic weight of sodium is 23 means that every
23 parts by weight of sodium in the compound represent one atom of CALCULATIONS FROM EQUATIONS
sodium.
We have seen already that the equation:
43 4
Thus 43.4 parts by weight of sodium represent —^- atoms of CuO + H,S0 4 -* CuSO« + H 2

sodium. Similarly for the other elements present:

(63.5 + 16) (2 + 32 + 64) (63.5 + 32 + 64) (2 + 16)
79.5 98 159.5 18
11.3 parts by weight of carbon represent — '-
atoms of carbon. means: 'One molecule of copper oxide reacts with one molecule of
sulphuric acid producing one molecule of copper sulphate and one
45'—3
45.3 parts by weight of oxygen represent — atoms of oxygen.
molecule of water.*
16 The appropriate molecular weights having been inserted, as above,
.*. Number of atoms represented is: it also means that 79.5 parts by weight of copper oxide react with 98

sodium carbon oxygon parts by weight of sulphuric acid, producing 159.5 parts by weight of

45.3
copper sulphate and 18 parts by weight of water. These 'parts by
43.4 11.3
weight' may be any desired weight-units grams, tons, ounces,
23 12 16
pounds, kilograms— provided that the same unit is used throughout.
or 1.89 0.94 2.83 Obviously, the figures given by the equation can be used to cal-
These cannot be the actual numbers of atoms present because culate any required information about the weights of the four sub-
fractions of atoms are impossible. We have to find the whole numbers stances concerned.
which are in the ratio 1.89 0.94 2.83. To do this, divide all these
: :
Example 1 . What weight of copper sulphate could be obtained by
figures by the lowest or, if this does not result in a whole number
starting with 10 g of copper oxide?
ratio, by the smallest difference. Then the number of atoms of each
element is
From the equation, 79.5 g copper oxide yield 159.5 g copper
sodium carbon oxygen sulphate.

L89 0.94 Z83 .". 10 g copper oxide yield 159.5 X -— g copper sulphate
0.94 0.94 0.94
or 2 1 3
= 20. 1 g copper sulphate
 :

58 A NEW CERTIFICATE CHEMISTRY CALCULATIONS FROM EQUATIONS 59

Example 2. What weight of pure sulphuric acid would be needed to We now have, on the left, 2S from the 2H 2 S (remember the 2
react with 15 tons of copper oxide? multiplies all the H 2 S) and S from the S0 2 therefore we must have ,

From the equation, 79.5 tons of copper oxide need 98 tons of 3S on the right and the balancing is complete.
sulphuric acid. 2H 2 S + S0 2 -»-2H 2 + 3S
.". 15 tons of copper oxide need 98 X -— tons of sulphuric acid Some such balancing process necessary for all equations, but
is

many of them become so familiar with frequent use that they can be
= 18.5 tons sulphuric acid set down correctly at once.
This means that equations have now been given a quantitative
meaning in terms of ordinary weight-units, instead of simply in terms Insertion of molecular weights into the equation
of atoms and molecules. This makes them extraordinarily useful for Here, is very desirable to remember that it is unnecessary to
it
making calculations of the weights of materials needed for chemical insert themolecular weights of any materials unless they are actually
reactions and the weights of products obtainable. Chemical manu- concerned in the calculation you are performing.
facturers base all their calculations of weights of materials on Consider, for example, this problem.
equations. Calculate the weight of calcium nitrate which would be formed by
We will now discuss the steps necessary in using an equation treating 148 grams of slaked lime, Ca(OH) 2 , with excess of dilute nitric
correctly for weight calculations of this type. acid.(Ca = 40; O = 16; H =1.)
Here the balanced equation is:
A balanced equation is necessary

has already been explained (p. 23) that, by a balanced equation,

It
Ca(OH) 2 + 2HN0 3
->- Ca(NO s) 2 + 2H 2

slaked nitric calcium water

we mean one which has the same number of each kind of atom on the lime acid nitrate
right of the equation as on the left. An unbalanced equation implies
that atoms have been created or destroyed; it is therefore wrong, In the problem, the only two substances mentioned quantitatively

and calculations based on it are certainly unreliable. The first and are calcium nitrate, of which a weight is to be calculated, and slaked

to obtain a balanced equation. lime, of which the weight is given. (Nitric acid is only mentioned as
absolutely essential step, then, is

Facility in producing balanced equations is only attainable with

'excess'.) The only molecular weights we need insert are, therefore,
those of calcium nitrate and slaked lime. 2HN0 3 and 2H 2 may be
practice, but this absolutely inviolable rule must be remembered:
ignored once the equation has been balanced, because the problem is
The formula of a compound is absolutely fixed and unalterable and an
equation must be balanced by taking appropriate numbers of molecules not concerned with them.

of the substances concerned, not by attempting alteration of their

So we get,

formula. Ca(OH) 2 + 2HN0 3 -*- Ca(N0 2 + 2H 3) 2

The following brief account will illustrate the process of balancing. 40 + 32 + 2 40 + 28 + 96
To obtain a balanced equation for the action of hydrogen sulphide, 74 164
// 2 S, on sulphur dioxide, S0 2
producing water, s O, and sulphur, S.
,
H From the equation, 74 g slaked lime yield 164 g calcium nitrate.
The skeleton, but unbalanced and incorrect, 'equation' will be:
H 2S + S0 2
-»- H 2 + S (UNBALANCED) .'. 148 g slaked lime yield 164 X — g calcium nitrate

We cannot alter any of these formulae or the symbols.

Now, both the oxygen atoms of the S0 2 molecule form water, = 328 g calcium nitrate
therefore 2H 2 must be obtained. This gives: Calculate the weight of lead which would be obtained by heating
H 2 S + SO -»- 2H sO + S (UNBALANCED)
a
34.25g of red lead in a stream of hydrogen and the weight of water
The 2H O on the right now requires 2H which must be provided
a 2,
formed at the same time. (Pb = 207; H = 1 ; O= 16.)

by taking 2H 2 S. This gives: Writing the balanced equation and inserting the molecular weights
2H 2 S + S0 2 -»- 2H 2 Q + S (UNBALANCED) of the materials concerned in the calculation, we have
 .

60 A NEW CERTIFICATE CHEMISTRY QUESTIONS 61

Pb 3 4 + 4H 2
-»- 3Pb + 4H,0 10. How many ounces of anhydrous zinc sulphate (ZnSO,) would be
red lead formed on completion of the reaction between 2 oz of zinc and dilute
+ 64 sulphuric acid containing 2 oz of the pure acid (HjSOJ? (N.U.J.B.)
621 4(2 + 16)
685 621 72 1 1 How many grams of hydrochloric acid, containing 20% by weight of
hydrogen chloride, would be required to dissolve 13 g of zinc? (N.U.J.B.)
(i) From the equation, 685 g red lead yield 621 g lead.
12. In a determination of the equivalent weight of carbon, 0.74 g of
34.25 the element was burnt in a current of oxygen, the products of combustion
.". 34.25 g red lead yield 621 X g lead were passed over heated copper(II) oxide, and the resulting carbon dioxide
685
was absorbed in potash bulbs. The increase in weight of the potash bulbs
= 31.05 g lead was 2.69 g. Calculate to two places of decimals the equivalent weight of
carbon.
(ii) From the equation 685 g red lead yield 72 g water. What was the object of using copper(II) oxide in this experiment? (C.)
34.25 13. A compound has the percentage composition N = 19.31%,
.-. 34.25 g red lead yield 72 x g water Ca = 27.58%, CI - 48.96%, and H = 4.13%. Calculate (a) the simplest
685
formula for the compound, (6) the volume which the nitrogen, present in
= 3.6 g water 14.5 g of the compound would occupy at s.t.p.
Atomic weights: N =
= 14, Ca = 40, CI 35.5, H= 1.A molecular
weight in grams of a gas occupies 22.4 dm 3 at s.t.p. (D.)
14. Give a brief account of the chemical reactions involved in the
QUESTIONS extraction of iron from its ores. 0.1867 g of a sample of iron containing
carbon as an impurity was dissolved in dilute sulphuric acid, filtered, and
All Atomic Weights required for these calculations can be found on the filtrate heated with a slight excess of concentrated nitric acid. An excess
p. 532.
of ammonium hydroxide solution was then added to the solution and the
1. How many tonnes of copper could be obtained by displacing copper
resulting precipitate was filtered off, washed, dried, and finally heated to
from copper sulphate solution by 16.25 tonnes of zinc? redness until the weight was constant. The weight of the product was
2. What weight of sodium oxide, Na s O, could be made from 1.15 0.2600 g. Give the reactions involved in this process and calculate the
g
sodium? percentage of iron in the original sample. (Fe = 56.) (L.)
3. Find the empirical formula: of the following compounds from their 15. Pure calcium carbonate contains 44% by weight of carbon dioxide.
compositions by weight: Some dried chalk weighing 0.4 g was dissolved in dilute hydrochloric acid.
(«) Zn, 47.8%; CI, 52.2% The carbon dioxide given off had a volume of 85.5 cm* measured at
(b) Na. 39.3%; CI, 60.7% 750 mm pressure and 12°C. Find:
(r) Cu, 39.5%; S, 20.3%; O, 40.2% (o) The volume of the carbon dioxide at s.t.p.
(«/) Pb, 62.5%; N, 8.45%; O, 29.05% (b) The weight of the carbon dioxide.
4. Calculate the percentage by weight of each element in the following (c) The percentage of pure calcium carbonate in the chalk.
compounds: (H = 1,C = 12,0 = 16. Weight of 1 dm' of hydrogen at s.t.p. = 0.09 g.)
(a) Sodium hydrogen carbonate, NaHCO, (N.U.J.B.)
(b) Calcium chloride, CaCI,
(c) Ammonium sulphate, (NH 4) 3 SO,
(d) Sodium thiosulphate, Na 2 S 8 O a
5. What weight of dilute nitric acid (containing 10% of the pure acid)
will be required to dissolve 5 g of chalk, calcium carbonate?
6. How many grams of hydrogen sulphide would be necessary to
precipitate 7.5 g of
copper sulphide from a copper sulphate solution?
7. 76.5 g of sodium hydrogen carbonate were heated strongly.
What
weight of carbon dioxide was obtained ? If a dilute acid had been added,
what weight of carbon dioxide would have been obtained in this case?
8. What weight of nitrogen dioxide could be obtained by heating
11.1 e
of lead nitrate?
9. 50 g of ammonium chloride were heated with 40
g of calcium
hydroxide. What weight of ammonia gas would be evolved ? Which of the
reagents is in excess and by how much?
 1

ATOMIC STRUCTURE 63

They are produced by all known gases and have been shown to have
-28 -10
a mass of 9.1 X 10 g and a charge of 1.6 X lO coulombs.
At the same time, positively charged particles leave the area of
the anode, their nature depending on the identity of the gas used.
Hydrogen, for example, yields hydrogen ions, H + The effect of the
Chapter 8 discharge is to ionise hydrogen atoms into electrons and hydrogen
.

ions.
Protons. Rutherford carried out experiments early this century in
which hydrogen was bombarded by fast alpha-particles (helium ions,
Atomic Structure; Shape of Molecules;
He 2+ ) from a radioactive source. He found that very penetrating
Kinetic Theory; Periodicity particles were produced, of approximate mass 1 ( C
12
12) and carry-=
ing an electrical charge equal to that of the electron, but positive. The
seems fairly certain that for most of the particles were named protons and are, in fact, the same as the posi-
nineteenth century,
IT
atoms were regarded as very small spherical tive particles produced in a hydrogen discharge tube (above). Alpha-
a very
particles like
minute lead shot. It was believed that no smaller particle could particles ionised hydrogen atoms by knocking out electrons from

exist, and that atoms were solid and homogeneous. This state of them.
affairs has been very greatly changed in recent years, mainly by the H-*H + -f-<?-
pioneer work of Lord Rutherford. Neutrons were discovered (1930) as a very penetrating radiation
It is now atoms are themselves built up from three
believed that knocked out of boron nuclei when this element was subjected to the
smaller particles— the proton, the electron and the neutron. The action of alpha-particles from the radioactive element, polonium. A
proton is a positively charged particle of mass about equal to that of a neutron has very nearly the same mass as a proton but no electrical
hydrogen atom. The electron is negatively charged, its charge being charge. This lack of electrical properties explains why neutrons were
equal but opposite to the charge on a proton. It has a very small detected so much later than electrons and protons.
mass, about 1/1850 of the mass of the proton. The neutron has no
charge, and its mass is about equal to the mass of a proton. Arrangement of these particles in the atom. Nuclear Theory
In 1906, Rutherford noticed that if a stream of alpha-particles was
Charge Mass ("C = 12) passed, as a very thin pencil, through gold leaf (of thickness about
proton -f- 1 one-millionth of a centimetre) and then on to a photographic plate,
electron —1 1/1850 a certain scattering of the alpha-particles was evident. Later (1909)
neutron nil 1

Discovery of these particles

Gold leaf
Electrons. In the late nineteenth century, a great deal of work was
done on the effects of electrical discharge at very high voltage (by
induction coil) through elementary gases at very low pressure. This ZnS
led to the discovery of cathode rays. These emerge at right angles to
screen
the cathode and travel in straight lines. If passed through an electro-
away from the negative plate, i.e., they
static field, they are deflected
The rays can exert mechanical pressure and
are negatively charged.
convey substantial amounts of kinetic energy so that a metallic
K- particles
object on which they impinge will be heated and may even dis-
integrate. From these facts, it was concluded that cathode rays
C^--^'
consist of a stream of negatively charged particles in rapid motion Fio. 15.
(about 10» cm/sec). These particles were given the name of electrons
Effect of gold leaf on alpha-particles.
62
 ;

64 A NEW CERTIFICATE CHEMISTRY ATOMIC STRUCTURE 65

Geiger and Marsden studied this scattering more accurately and Bohr was able to calculate the
several lines at definite frequencies.
extended the observations by using a zinc sulphide screen on a theoretical frequencies for such a spectrum and show that they
rotating arm. The screen scintillates when an alpha-particle strikes it.
accorded well with observed hydrogen spectra. It is also known that
It was found that the straight-line path of the great majority of the
spectra of other elements indicate similar electronic orbits in their
alpha-particles was little affected by the gold leaf but about one in atoms.
8000 of them was deflected through an angle of 90° or more from its
It was known that many cases occurred in which pairs or triplets
original direction. Rutherford commented later that, considering the
of spectral lines occurred close together, e.g., the two yellow lines of
thinness of metal used and the high velocity and mass of the alpha-
sodium. To explain these slightly varying energy levels in the same
particles, these large deflections were 'about as credible as if you had
electron shell, it was suggested that some orbits are circular and
fired a fifteen-inch shell at a piece of tissue paper and it came back
some elliptical, but this feature can usually be ignored for chemical
and hit you'. Rutherford deduced that these few large deflections of purposes, at any rate at the present level.
alpha-particles required atoms of gold to contain a region (the
This, and much subsequent work, leads to the following con-
nucleus) which:
clusions:
1. is positively charged because repels the positively charged 1. Several groups of electrons may occur in an atom and each
it

alpha-particles
group is known as an electron shell. Shells are numbered 1, 2, 3, etc.
2. is relatively massive and highly charged because the deflections
outwards from the nucleus. All electrons in a given shell have
are large;
approximately equal energy. This energy increases in successive
3. must occupy a very small space because so very few alpha-
shells outwards from the nucleus.
particles are materially affected.
2. The maximum possible number of electrons in a shell numbered
According to the current version of this nuclear theory of Ruther-
n is 2n 2 , i.e., in successive shells 2, 8, 18, 32, . . . electrons.
ford, protons and neutrons of an atom are concentrated into the
3. In the outermost shell of any atom, the maximum number of
nucleus which is, therefore, positively charged, relatively massive but
electrons possible is 8.
minute. The electrons, equal in number to the protons, and so making
A diagrammatic representation of a typical atom would be as
the atom electrically neutral, are outside the nucleus. The whole bulk
shown in Fig. 16.
of the atom, defined by the outermost electron ring, is very great
compared with that of the nucleus -in Rutherford's analogy about
the same proportion as the dome of St Paul's Cathedral to a man's
clenched fist.

Arrangement of electrons in the atom

Bohr (1913) put forward a theory of electron positioning which is

still generally accepted for chemical purposes.
It was developed
originally in connection with the hydrogen atom, which contains only Nucleus
one proton (as nucleus) and one electron. Bohr suggested the exist- \\\ Protons
ence of certain circular orbits (or shells) at definite distances from the 1
12 Neutrons
nucleus in which the electron may rotate. These orbits are associated
with definite energy content of the electron, increasing outwards
from the nucleus. While the electron adheres to any one orbit
(usually the innermost, of lowest energy), the atom radiates no
energy. If, however, the atom absorbs energy, the electron may jump
to one of the outer orbits of greater energy. If it later falls back to
the inner orbit of lower energy, energy will be radiated as light of a electrons revolving in orbits 2.8.1
definite colour (or frequency). Thus, if several outer, higher energy
Fig. 16.
orbits are involved, an optical spectrum should be obtained, showing
Sodium atom (diagrammatic).
66 A NEW CERTIFICATE CHEMISTRY ELECTROVALENT COMBINATION 67

The simplest atom is that of hydrogen. It consists of a single shells of non-metallic atoms with which the metal is combining. By
proton with one electron rotating round it. In order of complexity, this means, an electron octet is left behind in the metal and
created in
the simpler atoms are made up as in the following table, neutrons the non-metal. Both elements now have the outer electron structure
being omitted for reasons explained later: of a rare-gas, but the metallic particles have a positive charge
from
ELECTRONS the excess proion(s) left on the nucleus, while the non-metallic
ELEMENT PROTONS IN EACH SHELL particles are negatively charged from the added electron(s). The
hydrogen 1 1 particles are then known as ions.
helium 2 2
lithium 3 2 1
Thus:
beryllium 4 2 2
boron 5 2 3 Sodium atom Chlorinc atom
carbon 6 2 4
nitrogen 7 2 5 Protons Electrons Protons Electrons
oxygen 8 2 6 17
Before combination 11 2,8,1 2,8,7
fluorine 9 2 7
neon 10 2 8
sodium 11 2 8 1 17
After combination 11 2,8 2,8,8
magnesium
aluminium
12
13
2
2
8
8
2
3 Sodium ion -f- Chlorine ion —
silicon 14 2 8 4
phosphorus 15 2 8 5
sulphur 16 2 8 6 Both ions now possess stable outer electron octets, like a rare-gas.
chlorine 17 2 8 7
argon 18 2 8 8
No molecules of sodium chloride are formed. Because of the
+ and Cl~ ions for one
potassium 19 2 8 8 1 attraction of the oppositely charged Na
calcium 20 2 8 8 2 another, the ions arrange themselves into a rigid, solid shape called a
crystal, but they remain quite separate. No molecules of sodium
The number of protons on the nucleus (which equals the number of chloride form. The combination can only be expressed in ionic form
electrons in the shells) is called the Atomic Number of the element as Na + Cl~, meaning an association of sodium and chlorine ions in
equal numbers. For the sodium chloride crystal, see p. 371.
Types of chemical combination
From the table above, it will be seen that neon and argon have Characteristic properties of electro- (or polar-) valent compounds
eight electrons in their outermost electron layer, i.e., an octet of
(1) Polar compounds do not contain molecules. They
consist of
electrons. This structure is very stable
and extremely difficult to
aggregates of oppositely charged ions. In consequence, if they are
disturb. In consequence, these
two gases are chemically inert and
melted, or dissolved in water, to make the ions mobile, they conduct
form no compounds with other elements. They are self-satisfied. In
electricity and are, therefore, electrolytes (Chapter 13).
the simpler rare-gas, helium, the duplet of electrons is equally stable
(2) They are solids and do not vaporise easily.
and functions like the octet.
(3) They will not usually dissolve in organic solvents such as
The tendency of other elements is to try to attain this rare-gas
toluene, ether, benzene, etc.
structure of a stable outer octet (or duplet) of electrons and their
Salts, alkalis and bases arc electrovalent and acids, when in solu-
chemical behaviour is a reflection of this tendency. On this general
tion in water, also show electrovalency.
principle, elements combine in two main forms of combination,
known as the electrovalent (or polar-valcnt) and covalent types. The following cases are given in further illustration of electro-
valency.

Elcctrovalent Combination
Calcium chloride
(Also known
as polar-valent.) In this type, a metallic element or In the calcium ion, the two excess nuclear protons produce a
group loses, from its outermost electron shell, a number of electrons double positive charge; in each chlorine ion, the excess electron pro-
_
equal to its valency. These electrons pass over to the outer electron duces a single negative charge, i.e., Ca 2+ .2C1 .
 A NEW CERTIFICATE CHEMISTRY COVALENT COMPOUNDS 69

Calcium atom Two chlorine atoms electron passes from an orbit controlled by the nucleus of one
Protons Electrons Protons Electrons chlorine atom into an orbit controlled by the nuclei of both chlorine
Before combination 20 2,8,8,2 17 atoms. This joint control of the orbits constitutes the valency bond.
2,8,7
17
Other examples of molecules formed by covalency are shown in
2,8,7
Fig. 1 8. Each shared electron pair is made up of one electron from

each atom concerned. All the atoms obtain a shared octet or duplet
These valency electrons pass to the
of electrons. Each shared pair is represented by a stroke in the con-
chlorine atoms ventional formula, which is given for ethanol in illustration.

Calcium ion -f -f- Two chlorine ions -

Two separata Chlorine atoms:-
Protons Electrons Protons Electrons (M/e/eus(ft)/7 protons
After combination i and 18 (or 20) neutrons
20 2,8,8 17 2,8,8
(£/ectroia(o) 2-8-7
17 2,8,8

Calcium oxide

Calcium atom Oxygen atom Chlorine molecule CI-CI

Protons Electrons Protons Electrons
Before combination 20 2,8,8,2 8 2,6
shared
pair
I t FlO. 17.
These valency electrons pass to the
Chlorine atoms and molecule (diagrammatic).
oxygen atom

Characteristic properties of covalent compounds

Calcium ion -f- + Oxygen ion
(1) Covalent compounds consist of molecules. They contain no
Protons Electrons Protons Electrons ions, are unable to conduct electricity and so are non-electrolytes.
After combination 20 2,8,8 8 2,8 (2) Simple covalent compounds are gases or volatile liquids, e.g.,
ammonia, carbon dioxide, ethanol (alcohol). This is so because their
As stated on p. 67, the calcium ion acquires a double positive molecules are electrically neutral and have little attractive force for
charge; the two excess electrons produce a double negative charge each other. In more complex covalent molecules, e.g., naphthalene,
on the oxygen ion, i.e., Ca4+ .O s_ .
the atomic nuclei (+) of one molecule and the electrons (— ) of
Note the presence of the outer octet of electrons in all the above another attract each other. As the molecules come together, the
ions. electrons of each begin to exert repulsive forces on each other. The
forces of attraction and repulsion are balanced in the formation of a
Covalent Combination
crystal. These van der Waals forces are, however, rather weak and the
In this type of valency, electrons are not actually gained or lost by crystals have low melting-points (e.g., naphthalene 81°C) compared
the atoms concerned. They pass into a 'shared' state. with ionic crystals (e.g. Na+Cl", 801°C).
Consider two chlorine atoms. Each has the electron structure 2,8,7. (3) Covalent compounds are usually soluble in covalent organic
In covalency, the atoms contribute one electron each to a 'shared- solvents, such as benzene or carbon disulphide.
pair'. In this way, both obtain an approximation to the external Another variety of covalent bond (i.e., electron sharing) has been
octet by making fourteen electrons do the work of sixteen (Fig. 17). given the name of co-ordinate bond. This bond is characterised by the
Here, actual molecules are produced, not ions. Each 'shared-pair' fact that the two shared electrons are both supplied by one of the
 N H

70 A NEW CERTIFICATE CHEMISTRY COVALENT COMPOUNDS 71

-H Jt H electron duplet to the hydrogen nucleus while still maintaining

(though with sharing) the electron octet of the nitrogen atom. The
proton, combining with the NH 3 molecule, carries over its positive
charge to give the ammonium ion, NH 4
+ The co-ordinate bond
.

is often indicated by an arrow pointing from donor atom to

H H acceptor atom as shown, though there is certainly some internal
methane ammonia sfeom equalisation of the four bonds of NH« + This ion is associated
.

(electrovalently) with some anion as a salt, e.g.,

+ C1 _ or NH 4
H H
NH 4
+
NO,-.

u
<4
3 H H
ethonol
H— C—C—O-H
H H

• electron of
o electron of othe
H
in
Again, the ammonia molecule participates by co-ordinate bonding
the formation of the teirammine copper(Il) ion (also called

2+_
H
I

TH-N-H
-.2+

element H H H
Fig. 18. I I

Some covalent molecules.

or H— >Cu< N—
participating atoms (not one electron by each atom as in an ordinary 1
t I

covalent bond). A co-ordinate bond is formed (in simpler cases, at H

least) when one of the participants possesses a lone pair of electrons, ammonia H-N-H
i.e., a pair not directly concerned in molecule I
its existing valency bonds. This
lone pair donated to an atom needing them to build up, or com-
is
H
plete, an electron octet or duplet of great stability. The ammonia tetramminecopper (II) ion
molecule (Fig. 19) possesses such a lone pair of electrons; it can exer-
cise co-ordinate valency towards a hydrogen ion (proton) from an o electron of N
acid to produce the ammonium ion, 4 NH
+ This bonding supplies
. an • electron of H
Fio. 20.
o electron of N Tctramminc copper(lI) ion.

• electron of H
cuprammonium ion) which gives the intense blue coloration when
+ -1+ excess of ammonia is added to copper sulphate solution. In this
H r h r h ~i copper(II) sulphate, copper is in the 2,8,17,2 electron state with the
2-
outermost 2 (valency) electrons transferred to the SO* ion and the
H? N
J
+ H+-*- HI N 5H or H — N-MH1

outer electron shell vacant in the ion, Cu* + Four .

form co-ordinate bonds with the Cu i+ ion by means of their lone

NH
molecules 3

1
pair electrons to create a shared electron octet in the vacant valency
H H H
electron shell of the copper(II) ion (Fig. 20).
ammonia proton ammonium ion Oxygen, having a 6-electron outer shell and accepting a lone pair
molecule to complete the shared octet, is a frequent participant in co-ordinate
Fio. 19. bonds (as acceptor atom). A simple example of this is seen in the
Aimmonium ion. relation of phosphorus trichloride to phosphorus oxychloride.
72 A NEW CERTIFICATE CHEMISTRY MOLECULAR SHAPES 73

CI CI CI difference is applied to the ends of a metallic rod, the free electrons

lose theirrandom motion and move towards the positive end of the
rod, being steadily replaced by more from the source of P.D.
Hence
CI

(3 Cl
+ (°)- a Qys°ra -
Cl
P-MD
I

Cl
metals are good electrical
convey heat energy, metals
conductors.
are also
As
good
freely moving
conductors of
electrons
heat.

Since the bonding agent in a metal is mainly a moving electron

can

cloud, the ions of most metals will usually slide relative to one
o electron of P another, under stress, without shattering the lattice and produce a
• electron of Cl or new position of stability. This accounts for the malleability and
ductility of many metals, though special temperature conditions
Fig. 21.
may sometimes be necessary.
Phosphorus oxychloride.

Shapes of some Molecules

Compounds containing only co-ordinate bonds and covalent bonds
are very similar in properties to purely covalent compounds. Both Carbon dioxide
types are non-electrolytes (having no ions); the simpler examples are In a carbon dioxide molecule, the carbon atom is bonded to each
usually liquids in ordinary room conditions, but, with co-ordinate oxygen atom by two pairs of electrons in covalency. These electron
bonds present, tend to be less volatile. groups exercise mutual repulsion and produce a linear molecule.

Metallic bond oo o o
Metals are held together
o o
in solid crystalline form by metallic bond-
ing in something like the following way. The outer (valency) electrons o S C 2 o
• •
of each atom are only loosely held, being relatively distant from the 00
nucleus, and they separate from particular nuclei to move at random
o electron of Linear molecule
through the crystal lattice. The residual ions, now positively charged
• electron of C of C0 2
by loss of valency electrons, tend to repel each other but are held
together by the moving electron cloud and some overlapping of
residual electron orbits.
This type of bonding is very strong in some metals, e.g., iron,

which are difficult to shatter, but it is much weaker in, e.g., sodium
or potassium, which can be cut with a knife. If an electric potential

Molecular layer
+ atomic nucleus in cubic crystal

electron Fio. 23.

Carbon dioxide molecule and crystal.

In solid carbon dioxide, 'dry ice', these linear molecules take up a

Fio. 22. cubic formation (bonded by van der Waals forces). One layer of
Metallic bonding. molecules in the cube is shown.
74 A NEW CERTIFICATE CHEMISTRY MOLECULAR SHAPES 75

Steam
In a molecule of steam, the two hydrogen atoms arc bonded to the
oxygen atom by shared electron pairs and the oxygen atom has two
lone pairs of electrons not concerned in valency bonding. The two
lone pairs exercise a stronger mutual repulsion than that between
Iodine
Iodine produces a molecule, I 2 , by formation of a covalent (shared
pair)bond to which each iodine atom contributes one electron (so
completing, for each atom, a shared electron octet). By the operation
of van der Waals forces, the molecules then form crystals in which

H
H

H
GO
Covalent bonding in I2 molecule
Shape
molecule
of

{Valency electrons only)

o electron of o Bond angle Molecule of
• electron of H steam
Fig. 24.
Molecule of steam.

any other electron pairs present. The resultant effect of this is to

produce a 'bent' structure in which atomic nuclei all lie in the same
plane with 104±° as the H-O-H angle. If the four electron pair
repulsions were all equal, this angle would be 109±°.

Ammonia
An ammonia molecule contains three hydrogen atoms bonded
covalently, i.e., by shared electronpairs, to a nitrogen atom, which Layer of I 2 molecules in crystal.

Next layer covers dotted lines

,N Fio. 26.
H
h Iodine molecule and crystal.
h H' 107

they lie in a herring-bone pattern which is reversed in successive

H layers. One layer of iodine molecules is shown in the square. In the
o electron of N Bond angle in triangular pyramidal'
over the dotted lines.
next layer, molecules lie
• electron of H molecule
Methane
Fig. 25.
The four covalency bonds of the carbon atom in methane are dis-
Ammonia molecule.
tributed symmetrically in three dimensions, the angle between any
pair of valency directions being 1094°. Each bond represents a shared
has also one lone pair of electrons. The mutual repulsion of the four electron pair to which a carbon and hydrogen atom supply one
electron pairs produces a 'triangular pyramidal' shape of molecule electron each. The molecule of carbon tetrachloride is similar with
in which the H-N-H angle is 107° (not 109$° which would be pro- substitution of four chlorine atoms for the four hydrogen atoms of
duced if all four electron pair repulsions were equal). methane.
 H

76 A NEW CERTIFICATE CHEMISTRY FUNCTION OF NEUTRONS IN THE ATOM 77

H H corresponds to a high degree of unsaturation in the molecule. Each

carbon atom is also combined covalently with one hydrogen atom.
109^ The molecule is linear.

"0" 4\ FUNCTION OF NEUTRONS IN THE ATOM

H The above discussion of valency and chemical combination con-
o electron of C Symmetrical Shape of tains no mention of neutrons. They appear to have little influence on

o electron of H bond directions molecule the chemical properties of the atom. Their chief function is to help to
determine the weight of the atom. For example, the sodium atom,
FlO. 27.
with 1 1 protons and 12 neutrons, has a total weight of 23 units. The
Methane molecule.
Ethylene 1 1 electrons are relatively negligible in weight.
Many two atoms contain the same
cases occur, however, in which
In the ethylene molecule, C2H 4 , the two carbon atoms are com-
number of protons but numbers of neutrons. Having equal
differing
bined by two covalcnt bonds, i.e., two shared electron pairs. This
numbers of protons, these atoms must also have equal numbers of
indicates unsaturation in the molecule. Each carbon atom is also
electrons. These are arranged in the same way and give the atoms

H H identical chemical properties. But the differing numbers of neutrons

cause the atoms to have different weights. An element showing these
—
characteristic properties that is, possessing atoms of similar chemi-

>
H
\ H
cal properties but different weights —
is said to show isotopy and the

varieties of the atom are called isotopes of the element.

A well-known example of isotopy occurs in chlorine.

o electron of C Conventional Shape of

Isotope 1 Isotope 2
• electron of H structural formula molecule
Nucleus Electrons Nucleus Electrons
Fio. 28.
17 protons 2,8,7 17 protons .2,8,7
Ethylene molecule.
18 neutrons 20 neutrons
combined covalently to two hydrogen atoms. The nuclei of all six
atoms involved lie in the same plane, i.e., the molecule is planar. The 35 total weight 37 total weight
H-C-H angles are 117°.
t
Acetylene weights different chemical properties identical
In the acetylene molecule, C 2H a , the two carbon atoms are CI = 35 CI =
37
covalently combined together by three shared electron pairs. This

o Dalton believed that all atoms of the same element were exactly alike.
Isotopy has proved him wrong. But, except in a few exceptional cases,
elements contain isotopes in almost constant proportions and so
H^cic J
H H— C=C— appear to act as if all their atoms are equal in weight. Chlorine, for
o
o example, is found to have its isotopes mixed in such proportions that
its average chemical atomic weight appears constant. The lighter
o electron of C Conventional Linear isotope predominates, giving a value of 35.5.
• electron of H structural formula molecule It may also be mentioned that, in spite of recent, very prominent
Fio. 29. activities in splitting the atom, it can still be regarded as an in-
Acetylene molecule. divisible unit in chemical actions. Apart from modifications in the
 ;

78 A NEW CERTIFICATE CHEMISTRY KINETIC THBORY 79

electron shells, an atom is conveyed as a whole unit chemical
actions.
in
KINETIC THEORY
Uranium has two principal isotopes. Both possess 92 protons and Gases
92 electrons. One isotope has 146 neutrons, giving U = 238; the
was mentioned briefly at the beginning of Chapter 5 that a gas
other has 143 neutrons, giving U = 235. The lighter isotope con-
It
consists of molecules in rapid motion. The Kinetic theory makes the
stitutes about 0.7% of natural uranium. If the atom U = 235 acquires
following assumptions about a 'perfect' gas.
one extra neutron on the nucleus, it becomes unstable and divides
1. Molecules of a gas move in straight
lines at very great velocity
into two approximately equal parts. This 'fission' is accompanied
by with each other or with the wall of the containing
until they collide
a small diminution of mass, the combined final products having a
vessel. Gas pressure is exerted in this vessel as the result of collisions
mass slightly smaller than that of the uranium. Consequently, there
is a very great evolution of energy, principally as heat, according to between the gas molecules and the containing wall. The number of
collisions in unit time being very great, the pressure appears constant
the Einstein equation, E=
mc*, where E is the energy, m
the mass
lost and c the velocity of light. At the same time, neutrons (at constant temperature).
are
emitted. Other atoms of uranium absorb them and undergo fission, 2. The total volume of the actual gaseous molecules is negligible

relative to the capacity of the container.

so that, if the mass of uranium is large enough, a chain reaction is set
up, causing an atomic explosion. 3. Forces of attraction or repulsion between the molecules of the
Wehave noted already that the number of protons in the nucleus gas are negligible.
4. The average kinetic energy of the gas molecules measures the
of an atom is called the Atomic Number (Z) of the element concerned
the sum of the protons and neutrons in the nucleus is called
temperature of the gas.
the by real gases at
Mass Number (A) of the element and it also expresses the mass of the These assumptions are approximately fulfilled

ordinary temperature and pressure.

atom (on the scale of '|C =
12) to the nearest integer. If an element
is isotopic, it has as many mass numbers as
isotopes. The atomic Explanation of gas laws by the Kinetic Theory
weight of an element for practical purposes is the weighted average
Boyle's Law. If the volume of a given sample of gas is reduced at
of the accurate masses of its isotopes (on the same scale as above) as
they occur in the element in experimental practice. For a given constant temperature, the average velocity of the gas molecules remains
ele-
ment, atomic weight is always a constant, or very nearly so, except constant so they collide more frequently with the walls of the smaller
for products of radioactivity, such as lead (p. 492). In some containing vessel. The more frequent collisions cause higher pressure.
cases,
recent atomic weight tables show variations of atomic weight caused Charles's Law. Afall of temperature represents a decrease in the

by differences of isotopic distribution but, for ordinary purposes average kinetic energy of the gas molecules; that is average molecular
velocity decreases (mass remaining constant). At constant
pressure,
they are very slight, e.g., S =
32.064 0.003. ± of gas occupy a smaller
this decreased velocity causes the sample to

volume.
Example
Law of Partial Pressures. In a non-reactive mixture, each gas
Atomic Mass Number Neutrons Atomic exerts a separate pressure on the container because of collisions of
Number (A) protons A -Z Weight its molecules with the containing walls. The total pressure on the
(Z) protons + neutrons
is caused by the sum of all the
container collisions.

If gas pressure rises to very high values, molecules are

crowded
Chlorine 17 J|C1 35 18 35.46(3 atoms
(2 isotopes) very much more closely together so that ultimately forces between
J?CI 37 20 of35tolof
them are no longer negligible and their volume becomes significant
37 approx.)
relative to the space occupied by the gas. Then the simple
gas laws no

If an element X does not show isotopy, in the symbol, £X, a is the longer apply.
Mass Number and b the Atomic Number of any atom of X. For a set Solids
of isotopes of X, b is constant and a varies to express the variable
(atoms, mole-
number of neutrons per atom. Substances in the solid state are made up of particles
cules or ions) which are packed so tightly together as to leave only
 80 A NEW CERTIFICATE CHEMISTRY LIQUIDS 81

slight unfilled space in the mass of solid. (Contrast the very wide
separation of gas molecules mentioned above.) The particles are
bound together by forces strong enough to prevent movement of
translation so that a solid has a definite shape which remains fixed
(inconstant conditions) unless sufficient force is supplied to shatter or
distort the mass. Particles in a solid may however show a certain
amount of movement of vibration.
Particles involved in the assembly of solid structures may
following.
Atoms. Non-metals may form crystals by exercising covalency
1.
tocombine together very large numbers of their own atoms. An
example of such a solid is carbon as diamond, forming what is known
as a macromolecule. For a full account of this, and of the spatial
extension of the covalency of carbon that makes it possible, see p. 288.
Metals form solid masses in a different way. Their atoms can quite
readily part with valency electrons from their outermost shells,
as in
the following examples.
Na-»Na + +
e-; Cu -> Cu* + + 2e~
ferrous sulphide, some of the iron positions may be unoccupied and
this will cause the compound to deviate slightly from the Law of
Constant Composition.
Melting. If solids are heated, their constituent particles, atoms,
molecules or ions, acquire greater kinetic energy and vibrate more
violently. Eventually a point may come at which vibration overcomes
the binding forces and the particles become mobile. The crystalline
be the structure then collapses and a liquid state is reached in which the
particles are free to move. The temperature, t"C, at which this occurs
is called the melting-point of the solid and, at this
temperature (and
the prevailing pressure), the solid and liquid are in equilibrium.
(Melting-points are generally only slightly modified, i.e., lowered, by
moderate increase of pressure.) The energy which must be supplied
to convert the solid at r°C to liquid at f°C is known as latent heat of
fusion. Quantitatively, for example, 334 joules (80 cal) of heat energy
convert one gram of ice at 0°C to one gram of water at 0°C (at
standard pressure). If fairly simple molecules are only weakly bound
together in crystals by van der Waals forces, the melting-point of
the crystals will be quite low, e.g., naphthalene, C l0 H
g 8 PC. In,

The resulting positively charged ions

can then produce an ordered some cases, e.g., iodine, some molecules may break away from the
solid arrangement which depends on an equilibrium between crystal directly into the vapour phase. This is known as sublimation.
their
repulsive forces on each other and the binding efTect of the electron Ifbinding forces are strong, e.g., in electrovalcnt lattices such as that
cloud which moves, continually and at random, among of sodium chloride, or in some metallic crystals, melting-points will
them. See
also metallic bonding (p. 72).
be much higher, e.g., for sodium chloride, 801°C, and for copper,
2. Molecules. Many cases occur in which
non-metallic elements 1080°C, though sodium metal melts at only 97°C. When diamond is
form molecules by covalent combination, e.g., iodine as I heated in vacuo (to prevent burning), it does not melt because the
4 (For the
.

similar formation of a molecule Cl„ see p. 69.) In appropriate

condi- forces of covalency between the atoms are too great to be overcome
tions of temperature and pressure, the atomic
nuclei (+) of one by vibration with any ordinary source of heat. At very high tempera-
molecule and the electrons (-) of another molecule
attract each other ture, some carbon atoms will break away but by sublimation into the
sufficiently to bring about a close approach.
As the molecules come gaseous state, not by melting. (For determination of melting-point
together, the electrons of each begin to exert
repulsive forces on each see p. 217.)
other. The forces of attraction and repulsion
are balanced in the
formation of a crystal. These van der Waals
forces are, however
rather weak and the crystals tend to have low
melting-points. Simple
molecules of compounds, e.g., naphthalene, form Liquids
crystalline solids
by the operation of van der Waals forces in a similar way.
For further Ithas already been mentioned that, when the particles which make
account of the iodine molecule see p. 75.
up a solid acquire sufficient energy by heating, they become mobile,
3. Ions. When
elements combine by exercising electro-valency
the i.e., the solid melts and forms a liquid. The particles remain close
resulting positively and negatively charged ions exercise powerful together by virtue of the attractive forces between them but are
attractive forces on each other and can
form a solid crystalline perpetually in random motion. A liquid spreads to fill a containing
lattice. The arrangement of ions
in such a lattice can usually be vessel as far as possible but leaves a level liquid surface if the capacity
elucidated by X-ray diffraction. A
well-known example is the lattice of the vessel exceeds the volume of liquid. This occurs because the
of solid sodium chloride formed from the ions, Na +
and CI- for great majority of particles (usually molecules) at the surface are held
this see p. 371. Imperfect lattices sometimes occur. For example
in by attraction from the mass of particles below them; only relatively
82 A NEW CERTIFICATE CHEMISTRY
few particles of liquid (those with more than average energy) can
escape.
Because of the perpetual random motion of particles, usually mole-
cules, in a liquid, very small particles of insoluble solids are kept in
similar random motion in liquids because they are continually and
unevenly bombarded by molecules of the liquid. This motion is called
the Brownian Movement from its discovery by the botanist, Brown,
in 1827, in connection with pollen particles in water.
An ionic liquid is obtained when a crystal lattice of an electrovalent
solid breaks down by the action of heat but the temperature required
-
is usually far above room temperature, e.g., for K + C1 , 768°C. An
ionic liquid is an electrolyte, i.e., it conducts electric current by flow
of ions to cathode and anode and is decomposed in the process, e.g.,
K+ + e~ -» K (at cathode); CI" -* $CI a + e~ (at anode)
Amolecular liquid contains covalent molecules, e.g., carbon
tetrachloride, CC1 4 , chloroform, CHC1 3 carbon disulphide, CS 2 . A
, to achieve free formation of vapour bubbles; conversely, at pressures
great number of the simpler covalent compounds are liquid at room
temperature and pressure, i.e., the melting-points of the correspond-
ing solids are below room temperature. Such liquids are non-
electrolytes; they do not conduct electricity having no content of
ions.
Vapour pressure. All molecules in a liquid are subject to attractive
forces from neighbouring molecules. For molecules in the body of
the liquid, these forces balance each other but, for molecules at the
surface, there is a resultant attractive force acting downwards. In
spite of this,some molecules of greater than average energy can
escape from the surface of the liquid into the surrounding space and
are lost. The liquid is said to evaporate. Escape of these particles
high energy lowers the average kinetic energy of those remaining;
consequently, the temperature of the remaining liquid falls. This
coldness can be felt if a small quantity of a liquid such as ether is
allowed to evaporate on one's palm. Such a liquid, showing rapid
evaporation at room temperature, is said to be volatile and has a
low boiling-point, 36°C at standard pressure.
e.g., ether,
If a quantity of liquid contained in an otherwise evacuated,
is
sealed glass tube at a certain temperature, molecules will evaporate
from the liquid surface into the enclosed space. Since these molecules
are in rapid motion and cannot escape, some of them will collide
with the liquid surface and re-enter it. It is found that, as a result of
these opposite processes of evaporation and condensation, a state of
equilibrium is finally reached, provided some liquid is left. This
equilibrium is marked by the attainment of a vapour pressure which
is constant (for the given temperature) and is called the saturated
r PERIODICITY
vapour pressure of the liquid at that temperature. This saturated
83
vapour pressure is independent of the amount of liquid present (pro-
vided that it is not zero). For example, at 20°C, the saturated vapour
pressure of water is 17.5 mm.
Boiling. When a liquid is heated, its molecules acquire increased
kinetic energy; therefore, the proportion of fast molecules increases,
evaporation is more rapid and the value of the saturated vapour
pressure of the liquid rises. For example, for water at 40°C, it is
C
55.3 mm and, at 95 C, 634 mm. When a temperature is reached at
which the vapour pressure of the liquid equals the prevailing atmos-
pheric pressure, bubbles of vapour can form freely in the liquid and
rise to the surface. The liquid is said to boil. That is, the boiling-point
of a given liquid at a pressure of P mm
is the temperature at which
the vapour pressure of the liquid is P mm. For pure water at 760 mm,
the boiling-point is 100°C. At a higher pressure, water boils at a
higher temperature because a higher vapour pressure must be reached
below 760 mm, water has a boiling-point lower than 100°C, e.g.,
110°C at 1075 mm, 90°C at 526 mm. An apparatus for determining
boiling-points is given on p. 191.
Other liquids have different boiling-points at standard pressure.
For example, the binding forces between molecules of cthanol (alco-
hol) are such that the vapour pressure of this liquid reaches 760 mm
at 78°C, so this is its boiling-point at standard pressure. The boiling-
point ishigher than 78°C at pressures above 760 mm.
If a liquid contains non-volatile impurity in solution, this impurity
will occupy some of the surface of the liquid, hindering vaporisation.
Consequently, the vapour pressure is lowered at any given tempera-
of ture and the boiling-point of the solution is higher than the boiling-
point of the pure liquid at the same pressure; correspondingly, the
freezing-point of the liquid is depressed by non-volatile impurity. For
example, 3 g of sodium chloride raise the boiling-point of 100 g of
water by about 0.5°C and depress the freezing-point by about 2°C at
standard pressure. This is why sea-water is much less readily frozen
than fresh water in cold weather and why addition of common salt
causes ice or snow to melt at temperatures not too far below 0°C. An
experiment illustrating the effect of sodium chloride on the boiling-
point of water will be found on p. 216.
PERIODICITY
Neglecting hydrogen, which has a uniquely simple atom (one pro-
ton and one electron), the lightest atoms have, in order of atomic
number from left to right, the following electronic structures.
84 A NEW CERTIFICATE CHEMISTRY PERIODICITY 85

Group O IV V VI The NCl a and PCl a are both covalent liquids, non-
chlorides,

NO VII ,
I II III
electrolytcs and rapidly hydrolysed by water. Both the hydrides,
He Li Be B C F NH S and PH a form salts with hydrogen chloride, NH 4 C1 and
,
Period 2 2 2,1 2,2 2,3 2,4 2,5 2,6 2,7
PH 4 C1, though the latter is much less stable, decomposing at about
Ne Na Mg Al Si P S CI
35°C.
Period 3 2,8 2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7
The occurrence of successive groups of elements showing strong
Ar K Ca chemical similarity in this way because of their similar outer electron
Period 4 2,8,8 2,8,8,12,8,8,2
shells is called periodicity. The Periodic Law has been developed fully
to include all known elements and is expressed in a general Periodic
It willbe seen that, arranged in this way, elements in the same vertical
Table, of which the above arrangement is the earliest part. Period 1
columns have the same number of valency electrons in the outermost
(not shown above) is allotted to hydrogen only and Periods 2 and 3
shell of their atoms. Because of this, the elements in each column tend
follow as given on p. 84. The Groups of the table (written vertically)
to resemble each other closely in chemical behaviour. For example,
arc numbered by Roman numerals, O-VII. See the complete Periodic
the rare gases. He, Ne and Ar, show a chemical inertness which is
Table printed in the front endpaper.
determined by the stable outer electron octet or duplet. These gases
The more important of the Groups have already been considered
form no compounds with other elements.
briefly for the elements of Periods 2 and 3. Group VII is the halogen
Sodium and potassium, each with one electron in the outer shell,
group; of its members, fluorine and chlorine have been shown in
resemble one another very closely. Both are univalent, ionising by
Periods 2 and 3 and bromine and iodine follow in later periods. This
the loss of one electron per atom. Both are powerful reducing agents
Group is important enough to be given rather special consideration.
and good conductors of electricity.
Its members show marked general similarity of properties and also,
Na -> Na + + e~ (K similar) in many instances, a consistent gradation of behaviour.
Both are strongly electropositive, attacking cold water with liberation
of hydrogen. Group VII (Halogens)
Na + H tO -» Na+OH- + iH, (K similar) These elements and the electronic arrangements in their atoms are:
Both form strongly basic oxides, Na 2 and K 0, and soluble hydrox-
2 F2.7 CI 2,8,7 Br 2,8,18,7 12,8,18,18,7
ides, NaOH and KOH, which are strong alkalis. The carbonates, Atomic number 9 17 35 53
Na 2CO a and K s CO a are both soluble in water, giving mildly alkaline
,

solutions,and are unaffected by ordinary heating. The nitrates of
both metals liberate oxygen when heated and leave a nitrite.
2NO a --»-2N<V + 0,
Lithium resembles sodium and potassium in electropositive char-
acter and univalency, giving the ion, Li f . It also gives a solid, electro-
-
valent hydride, Li + .H and attacks water liberating hydrogen, but
only slowly. In this and in its almost insoluble carbonate and fluoride,
it differs considerably from sodium and potassium and has some
resemblance to the less electropositive calcium of Group II.
Similarly, nitrogen and phosphorus show marked chemical similarity
as non-metals. Both exercise a maximum valency of 5 (i.e., the number
of outer valency electrons) and also a lower valency of 3 (i.e., the
octet — 5).
These valencies appear in N 2O s and P 4 O 10 and in NH 3
The marked similarity of their chemical properties depends es-
sentially on their possession of the same number (7) of electrons in
the valency (highest energy) shell, but a pronounced gradation is
imposed on the general similarity as the atoms increase in com-
plexity from fluorine to iodine.
All the elements exhibit a valency of one in covalent combination
with hydrogen and in electrovalent combination with metals. By
formation of a shared electron pair with hydrogen in the first case,
and capture of an electron from a metallic atom in the second, all
these elements complete the external electron octet. Similarly,
by
formation of one shared electron pair, all produce diatomic mole-
cules.
,
H, + X 1 ->2HX; X + 2e--^2X-; 2X-+X.
2

and PH 3 Both the oxides are strongly acidic and combine with
.
where X is F, CI, Br or I.
water to form acids, HN0 3 and HPO a .
Being electron acceptors, all the halogens are oxidising agents.
Examples are the following.
NjO B + H»0 —* 2HN0 3 (P 4O 10 similar)
86 A NEW CHRTIFICATB CHEMISTRY periodicity 87

2Fea+ + Cl s -*- 2Fe» + + 2C1~ (iron(II) to iron(III)); Br, similar is insoluble in water, the calcium salts of the other three halogens
S»- + Br a —* 2Br- + S (H a S to sulphur); Cl 2 and I2 similar (CaCl 8 , CaBr», Cal 2 ) are very soluble and deliquescent. Also, silver
fluoride is quite soluble in water while the other three silver salts
As the number of electron atoms increase in size
shells increases, the
from the (AgCl, AgBr, Agl) have very low solubilities indeed. Also chlorine
Since each electron layer
smallest, F, to the largest, I.

screens the outermost electrons from the attractive power of the forms an oxide, C1 2 7 which is the characteristic oxide for a
,

nucleus, we should expect electrons to be most firmly held (or at- Group VII element. None of the other halogens forms such an oxide.
tracted) by fluorine atoms and least firmly held (or attracted) by
The highest oxide of iodine is 1 2 6 and of fluorine, F 20, while
iodine atoms. That fluorine should be the strongest,
bromine forms no stable oxide at all. On strict gradation, bromine
is, and iodine the
would be expected to be intermediate between chlorine and iodine in
weakest, in oxidising behaviour. This is actually so. For example, in
the order, F —* CI —> Br — >• I, each halogen can oxidise the ions of
solubility in water but, in fact, it is the most soluble of the three (with
iodine the least soluble). Fluorine attacks water rapidly at room
those which follow it and liberate the free halogen. Examples are the
temperature, liberating a mixture of ozone, 3 and oxygen. (For
,
following.
some further halogen comparisons relating to Cl 2 , Br 2 and 1 2 only,
Chlorine liberates bromine from potassium bromide solution:
see p. 385.)
CU + 2Br--*-2Cl- + Br,
Bromine liberates iodine from potassium iodide solution:
Progression of properties in a Period
Br a + 2I--^2Br- + I !1
The progression of properties for elements in the same period can
There is a similar gradation from F to I in vigour of oxidation of
be illustrated from Period 3.
hydrogen at room temperature.

Fluorine combines explosively even in the dark; Period 3 (Groups in Roman numerals)
Chlorine combines slowly in daylight; I II III IV V VI Vll
Bromine combines slowly in sunlight; Ne Na Mg Al Si P S CI
Iodine combines only when heated and then slowly and 2,8 2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7
partially.
The figures represent the electron groupings in the various atoms,
The same gradation found in the stability of the hydrides towards
is
left to right being outwards from the nucleus.
heat and in the heat of formation of the sodium salts. The chemical inertness of neon, resulting from its very stable outer
electron octet, has already been noticed (p. 84).
% dissociation Heat offormation
at 720°C inkJ
Elements of Groups I to III
HF nil NaF 568
The elements of Groups I, II and III (Na, Mg, Al) all
Elements.
HC1 0.0013 NaCI 410
show marked metallic character by ionising with electron loss but
HBr 0.2 NaBr 360
the metallic character weakens in the direction Na —* Mg —* Al.
HI 28.0 Nal 288
The valency of each element is equal to the Group number of the
element and to the number of electrons in the outermost (valency)
Another illustration of the F—>I gradation is given by the
shell.
boiling-points at standard pressure of the four halogen elements,
which are: Na-*Na+ + e-; Mg -»- Mg a+ + 2e~; Al -* Ms+ + 3e~
Sodium hydrogen from cold water, showing its exception-
liberates
F2 CI, Br, I.
ally electropositive nature; the other two metals liberate hydrogen
-188 -33.5 59 184 (all °C)
from dilute acid. In all these cases, hydroxonium ion is reduced by
halogen pro- electron gain.
It must be allowed, however, that, in certain respects,
perties do show some variation. For example, while calcium fluoride 2H.O+ + 2e~ -+• 2H,0 + H,
88 A NEW CERTIFICATE CHEMISTRY
PERIODICITY 89
Chlorides. The
chlorides of sodium and magnesium are electro-
lytes, Na + Cl~ and Mg
2+ (C1~) . Both are soluble in water; sodium number). Acceptance of more than two electrons per atom never
2
occurs.
chloride is chemically unaffected by water but magnesium chloride

is hydrolysed slightly, showing the somewhat weaker electropositive

S-|-2e--»-S«-; CI + «"-»- Cl~
(metallic) character of magnesium. Aluminium is still less character- This valency pattern is typical of non-metals.
Chlorides. The elements of Groups IV and V each produce a
istically metallic in its chloride. When anhydrous, the chloride is
covalent (as A1 2 C1 6 ) and is much hydrolysed by water, i.e., resembles chloride by utilising covalency numerically equal to the Group num-
the chlorides of non-metals, but it yields ions in aqueous solution, ber, Le., SiCl 4, PCI B Both are rapidly hydrolysed by water with
.

-
Al 3+ (hydrated) and CI as metallic chlorides do. liberation of hydrogen chloride and, when pure, both are non-
electrolytes.

--H P0
Oxides. The oxides of sodium and magnesium are electrovalent
compounds, (Na + ) 2 2- and Mg2+ 3- Both are soluble in water and .
SiCl 4 + 4H 2 Si(OH) 4 + 4HC3;
yield alkaline solutions by forming hydroxide ions. The more elec- PC1 6 + 4^0 3 4 + 5HC1
tropositive sodium gives by far the stronger alkali. The same elements also produce chlorides by exercising covalency

Oa " + H 2 -»- 20H~ of (8 — Group number), Le., SiCI 4 (as before) and PC1 3 This .

trichloride is a covalent liquid, non-electrolyte and rapidly hydro-

Aluminium oxide has basic properties, e.g., in the reaction
lysed by water.
A1 2 8 + 6HC1 -»- 2A1C1 S + 3H 2 PC1 3 + 3H aO -* H 8 PO s + 3HC1
but forms no alkali with water and so shows itself less electro-
it Contrast the metallic type of chloride produced at the other end of
positive than sodium or magnesium. Further, aluminium oxide the period in Groups I and II, where the elements have 1 or 2 valency
shows slight acidic tendency (and is, therefore, amphoteric) by form- electrons per atom and produce electrovalent chlorides, solids,
ing an aluminate with caustic alkali. This resembles the behaviour electrolytes if molten or in aqueous solution, and either unaffected,
of a non-metal. or only slightly hydrolysed, by water.
A1 S 8 + 2NaOH + 3H 2 -> 2NaAl(OH)4 Oxides. Elements of Groups IV to VII all form an oxide by exercis-
Hydride. Sodium (heated
dry hydrogen) forms a solid, electro-
in ing covalency equal to the Group number, i.e., SiO g P 4 O 10
, S0 3 ,

valent hydride. This occurs because the metal is so strongly electro- and C1 2 7. When combined with water, all these oxides produce acids.
positive as to reduce hydrogen by donating electrons to it. This is characteristic of non-metals.

2Na +H ->-2(Na + H-) Si0 9+ H O ^ H Si0 3

g 2 P4 + 2H -> 4HPO„
-
; 10 2
2

This hydride yields hydrogen with cold water and is an electrolyte SO a + H 8 -> H 2S0 4 ; C1 2 7 + H gO 2HC10 4
when molten, giving hydrogen at the anode. (Compare hydrides in In addition, phosphorus and sulphur also form well-known oxides
Groups IV to VII later.) by exercising a lower covalency, i.e., P 4 0„ and S0 2 These are also .

H~ + H aO -> OH- + H 2; 2H~ ->- H 2 + 2er (to anode) acidic oxides.

P 4Og + 6H 2 -* 4H 8P0 8 ; SO a + H2 «* H S0 8
a

Elements of Groups IV to VII (Si, P, S, CI) Contrast the oxides with basic properties formed by the metals at the
other end of the Period, Na 2 and MgO.
In Period 3, all the elements of Groups IV to VII exercise covalency
Hydrides. Elements of Groups IV to VII all form hydrides by
numerically equal to their group number by using the valency
electrons to form covalent pairs, e.g., in oxides SiO s , P 4 O 10 SO s
utilising covalency equal to (8— Group number), U., SiH 4 , PH 3 ,
, ,
H 2S, HC1. AH these are typical of simple covalent compounds, i.e.,
C1 2 7 . Oxides with lower oxygen content also occur, e.g., P4 6 SOz , ,
gaseous at ordinary temperature and pressure and non-electrolytes
C1 2 0. In addition, each element exercises a covalency of (8 — Group
when water-free, having no chemical reaction with water (except
number), e.g., in hydrides SiH 4 PH 3 H 2 S and HO. Electro-valency is
, ,
ionisation by HjS and HCI). Contrast the metallic hydride formed by
shown by elements of Groups VI and VTI only. This is exercised by sodium at the other end of the Period -electrovalent (Na + H-), an
acceptance of electrons to complete the outer octet and so form a
— electrolyte when molten (yielding hydrogen at the anode), attacked
negative ion. This electrovalency is numerically equal to (8 Group by water to yield hydrogen.
 .

90 A NEW CERTIFICATE CHEMISTRY QUESTIONS 91

In physical properties, the Group I-III elements of Period 3 Zinc compounds, iron(II) or ferrous compounds, copper(II) or
(Na, Mg, AT) are all metallic, e.g., good conductors of heat and cupric compounds and lead(II) or plumbous compounds have ions
electricity. The Group V-VTI elements of Period 3 are non-metallic and formulae like those of calcium.
in type, e.g., very poor conductors of heat and electricity. Iron(III) ox ferric compounds have ions and formula: like those of
Notice the following patterns in Period 3 which are repeated in aluminium.
other periods.
Group Recent Modifications of Dalton's Atomic Theory
i n in iv v vi vn o 1 Elements are made up of small, indivisible particles called atoms
Valency towards
ClorH 123 432 1- The atomic nature of elements is not disputed. Atoms can, how-
ever, no longer be regarded as indivisible in the full meaning of the
Valency towards term. Radioactive elements are spontaneously dividing in the sense
O (maximum) 12 3 4 5 6 7 — that the atomic nucleus is giving out particles and so producing two

Electropositive (metallic) less complex atoms, e.g., radium disintegrates to produce two rare
* gases, helium and radium emanation (radon).
character increasing

Electronegative (non-metallic)
2. Atoms of a given element are all exactly alike
> This statement can no longer be accepted. The phenomenon of
character increasing
isotopy (p. 77) contradicts it. Thus, potassium has isotopes 39 K=
It is important to know accurately the chemical formula: of the
and K. =
41. Both have 19 nuclear protons and 19 electrons, arranged
2. 8, 8, 1, so have the same atomic number and properties. But the
chief compounds of the common metals. They are listed below (by
41-isotope has two extra neutrons on the nucleus and so has the
groups of the Periodic Table) for study and reference.
heavier atom. Most elements exhibit isotopy in this way, (See also
p. 78.)
Group of P.T. I n ra
3. Atoms cannot be created or destroyed
Li, Na, K Mg, Ca,Ba Al This statement is still acceptable when applied to chemical re-
actions, in which, apart from electronic changes, atoms react as whole
Valency 1 2 3 units. The changes associated with atomic fission, however, certainly
Ion Na+ Ca ! + AP+ destroy atoms of the element involved, in the sense that the nuclei are
Oxide (Na+)2 O a -
Ca ! +O a - 3
(Al +)a(0»-) 3
Hydroxide Na+OH- Ca'+(OH-) a Al 8 +(OH-) 3 broken into smaller units which correspond to simpler atoms. For ex-
Chloride Na+CI" Ca J +(CI-) s Al a a 8 (covalent) ample, the nucleus of the uranium isotope, U =
235, can absorb
Sulphate (Na+) 8S(V- Ca'+S<V- (Al s +) a(S(V-)s a neutron and then break up into two roughly equal parts, which are
Nitrate Na+NO," Ca»+(N0 3 -) 3 Al a +(N03 -) 3 nuclei of atoms in the neighbourhood of barium (Ba 137). =
Carbonate (Na+) 2 CO s "- Ca'+OV- none
Hydrogen Atoms combine
4. in small whole numbers
carbonate Na+HCO," ca^co,-), none
Sulphide (Na+^S'- Ca 2+ S 2 - (A1»+) 2 (S«-) S This statement is still acceptable for most elements. Carbon,
(decomposed by however, forms the very complex compounds of 'organic' chemistry
water)
(p.319) and the element, silicon, occurs in some very complex silicates.

The ionic formula: are shown in most cases though the molecular
forms are often written, e.g., NaOH, Na 2 S0 4 , Ca(N0 3 ) 2 .
QUESTIONS
Ammonium salts have formula; like those of sodium salts, with 1. What are the three particles which make up ordinary matter?
ion, NH
+
4 , instead of Na
+ There is no oxide.
. Tabulate their relative charges and masses. State briefly how they are
92 A NEW CERTIFICATE CHEMISTRY QUESTIONS 93

arranged in a typical form of elementary matter and illustrate your
ment by a diagrammatic representation of one atom of it.
2. The compounds named below are all covalent compounds. With the
help of the table of electron-structures on p. 84, give a diagram for a mole-
cule of each of these compounds, showing the outermost electron shells
only: (i) carbon tetrachloride, CC1,; (ii) phosphorus trichloride, PC1 3
(iii) silicomelhane, SiH«; (iv) chloroform, CHC1,; (v) phosphine, PH,;
state- 10. By
reference to the properties of (a) the elements, (b) their oxides,
(c) theirchlorides, justify the inclusion of (i) sodium and potassium, (ii)
nitrogen and phosphorus in the same group of the Periodic Table.
1 1 Taking the symbol, l86 X, to represent an atom of the element X,
state (a) the atomic number of X, (6) the number of neutrons in an atom
; of X, (c) the number of electrons in an atom of X, (d) the mass number of
X. If another atom is represented as g X, what term would be used to state
8
>

its relation to ', X and what is the difference between them in terms of
6
(vi) methylene chloride, CH,Clt .

3. The following compounds are electrovalent. With the help of the the number and situation of particles present ? If a sample of X contained
table of electron-structures on p. 84, state what electronic changes take 90% of 'g'X and 10% of '88 X, show that the chemical atomic weight of X
place when they are formed from their elements: (i) lithium oxide; (ii) would be 16.2.
potassium chloride; (iii) magnesium oxide; (iv) sodium sulphide. State 12. What feature of the atomic structure of the four halogen elements,
briefly what kind of properties you would expect all these compounds to fluorine, chlorine, bromine, iodine, justifies their common inclusion in
show by virtue of their electrovalent character. Group VII of the Periodic Table ? State and explain in electronic terms what
4. Explain the term isoiopy and illustrate by reference to one actual valency behaviour they all share. Bromine is said to be intermediate in
example. Explain how this phenomenon contradicts a certain part of behaviour between chlorine and iodine. Justify this statement by reference
Dalton's Atomic Theory of 1808. Why, in spite of this contradiction, was to two examples of the chemical behaviour and one example of the physical
the Atomic Theory apparently in accord with experimental experience? behaviour of these three elements. Mention one respect in which bromine
is not the intermediate element of the three and two features of the chemistry
Explain briefly the difference between electrovalency and covalency.
5.
Of which of these two types of valency is ammonia an example? By a of fluorine in which it differs from the other three halogen elements. If
astatine is another element of this Group (following iodine), give one
simple electronic diagram show the essential structure of the ammonia
molecule. (Give a key to your diagram to explain any symbols used.)
chemical property you would expect it to possess and briefly justify your
choice.
(N.U.J.B.)
6. Complete the following table. 13. Explain briefly in electronic terms why (1) the ammonia molecule,
(2)the oxygen atom can participate readily in co-ordinate bonding. Give
Atomic Mass an example of the formation of an ion from ammonia by this means. Show,
Element Protons Electrons Neutrons by electronic diagram, the formation of a co-ordinate linkage between
Number Number
phosphorus trichloride and oxygen. State one difference of chemical or
physical behaviour you would expect between (i) phosphorus trichloride
X 11 12 and its co-ordinate compound with oxygen, (ii) phosphorus trichloride and
Y 6 6 potassium chloride. Briefly explain your choice.
Z 8 16
14. Suppose that elements W, X, Y, Z are all in the same (early) period
of the Periodic Table. Allot them to their correct Groups on the following
7. Suppose that elements with chemical symbols. A, B, D, appear in the evidence: an oxide, W,0 exists and is strongly basic; forms a liquid, X
same early Period of the Periodic Table and in Group I, III and V respect- covalent chloride, XCIj; the oxide of Y -
is Y,O a ; Z produces an ion, Z .
ively. Answer the following questions:
Write empirical formula for (a) the basic oxide of A, (b) the sulphate
(1) (1) What would be the effect of adding W,0 to water and then spotting
of B, oxide of D.
(c) the characteristic the liquid on to universal indicator paper? Explain. Write an ionic formula
(2) Two of these elements form ions. Write symbols for these ions, for the sulphate of W. Briefly characterise the hydride, WH.
showing electrical charges. (2) Write the formula of the highest oxide of X and an equation for its
(3) Which of these elements is likely to produce an amphoteric oxide? likely behaviour with water. If X forms a lower oxide, what is its likely
Define this term. formula? What is the formula of the simplest hydride of X and its likely
(4) Which of these elements is mostly likely to (a) liberate hydrogen from physical state at s.t.p. ? Relate this to its valency type.
water, (b) form a solid hydride, (c) form a gaseous hydride? Write a (3) Write the empirical formula of the chloride of Y. Discuss (briefly)
formula (ionic where appropriate) for each of these hydrides. likely behaviour of this chloride with water. The oxide, Y,0 3 , is amphoteric.

8. (i) In the reaction: Zn + Cu* + —> Zn ,+ + Cu, which reagent is Explain this term.
oxidised and why? In the reaction: Cl 2 + 2Br"
(ii) —> 2CI~ + Br„ which (4) What is the likely behaviour of the element Z in the field of oxidation-
material is the reducing agent and why? Answer in electronic terms in reduction? Explain in electronic terms. Write an ionic formula for the
both cases. compound formed between Wand Z. Estimate qualitatively its melting-
Explain the meaning of the term: metallic bond. Explain why a
9. point and describe the effect (if any) of an attempt to pass electric current
typical metal is (a) a good conductor of electricity, (b) a good conductor of through this compound (i) at room temperature, (ii) above its melting-
heat, (c) in some conditions at least, malleable and ductile. point.
94 A NEW CERTIFICATE CHEMISTRY
15. State, without diagrams, what numbers of electrons occur in the
successive electron layers of the atoms of (a) carbon, (b) oxygen, (c) nitro-
gen, (d) chlorine. By diagrams, show the arrangement of valency electrons
in the molecules of (i) H,0, (ii) ammonia, (iii) carbon dioxide, (iv)
ethylene, C,H 4 Sketch the shape of each molecule. Why (in electronic
.

terms) is chlorine a posverful oxidising agent?

16. Show by simple diagrams the arrangement of valency electrons in
Chapter 9
the molecule of (a) methane, (6) acetylene, C»H,. Sketch the shape of each
of the molecules. Comment on the following facts: (i) the molecules of
methane and carbon tetrachloride resemble each other very closely in
shape, (ii) the boiling-points (at standard pressure) of these compounds Molecular Theory
are: methane, 1 12 K, carbon tetrachloride, 350 K.

The Gas Laws

WE have already seen (Chapter 6) that the behaviour of gases

when subject to temperature and pressure change, can be ex-
pressed by two simple laws, those of Boyle and Charles.
Boyle's Law. The volume of a given mass of gas is inversely pro-
portional to its pressure, temperature remaining constant.
With the usual symbols, this is expressed mathematically as:
pv = a constant (T constant)
Charles' Law. The volume of a given mass of gas is directly pro-
portional to its absolute temperature, pressure remaining constant.
With the usual symbols, this is expressed mathematically as:

— = a constant (p constant)

Gay-Lussac's Law of gaseous volumes

A third law, describing the behaviour of gases, when involved in
chemical reactions, was stated by Gay-Lussac.
We can illustrate the Law of Gay-Lussac by quoting first some of
the experimentally observed results of chemical reaction between
gases, upon which the law is based. Temperature and pressure are
to be considered constant throughout each statement.

1. Ammonia.
2 volumes of ammonia decompose to give 1 volume of nitrogen
and 3 volumes of hydrogen.
2. Steam.
2 volumes of hydrogen combine with 1 volume of oxygen, giving
2 volumes of steam.
3. Hydrogen chloride.
1 volume of hydrogen combines with 1 volume of chlorine to
give 2 volumes of hydrogen chloride.
95
96 A NEW CERTIFICATE CHEMISTRY
4. Nitricoxide {nitrogen monoxide)
2 volumes of nitric oxide decompose to give 1 volume of nitro-
gen and 1 volume of oxygen.
Examining these experimental results (the methods by which they
have been obtained are given in Chapter 1 1), we notice at once that
all the volumes of the gases concerned are related to each other by
simple whole number ratios.
Whenever gases are concerned in chemical action, simple whole-
number relations between their volumes are always found. This is the
fact which was first noted by Gay-Lussac and expressed in his Law of
Gaseous Volumes, which is now stated.
Gay-Lussac's Law of gaseous volumes. When gases react they do so in
volumes which bear a simple ratio to one another, and to the volume of
the product if gaseous, temperature and pressure remaining constant.
Simple behaviour of gases: an explanation required
These three Laws of Boyle, Charles and Gay-Lussac express among
—
them a highly interesting fact about gases a curious similarity of
behaviour. In chemical properties, and such physical properties as
density and solubility in water, gases show marked variations. There
are neutral gases such as nitrogen, oxygen and hydrogen, acid-
producing gases such as sulphur dioxide, hydrogen chloride and
nitrogen dioxide, alkali-producing gases such as ammonia; gases of
very high solubility in water, such as hydrogen chloride (500 volumes
of gas dissolve in 1 volume of water), gases of moderate solubility,
such as hydrogen sulphide (3 volumes of gas dissolve in volume of
1
water) and gases of very low solubility, such as nitrogen (0.02 volumes
dissolve in 1 volume of water); some gases are chemically very
reactive, e.g., chlorine, and some are entirely inert, e.g., argon. But,
however great the variations in these properties may be, all the gases
obey the Laws of Boyle, Charles, Gay-Lussac. There must be some
explanation of this similarity. Note that it does not matter whether
the gas is an element, e.g., hydrogen, or a compound, e.g., hydrogen
chloride; each obeys the laws equally well.
Avogadro's Hypothesis
The explanation was put forward in 181 1 by Avogadro, an Italian
form known as Avogadro's Hypothesis. We have
scientist, in the
seen in Chapter 2 that the smallest particle of an element or com-
pound which can exist separately is called a molecule of it. Avogadro's
explanation of the simple behaviour of gases, especially as expressed
in Gay-Lussac's Law, was that equal volumes of all gases, under the
same temperature and pressure conditions, contain the same number
of molecules. When this suggestion was put forward it was purely a
MOLECULAR THEORY 97
hypothesis, that an idea which had occurred to Avogadro, which
is,
appeared to him which still required to be tested further
sensible, but
before it could be fully accepted. The truth of it has since become
experimentally demonstrable, and it is frequently known, on that
account, as Avogadro's Law. (See Avogadro Constant, p. 107.)
Avogadro's Law. Equal volumes of all gases at the same temperature
and pressure contain the same number of molecules.
This law has been of the greatest value in the development of
chemistry since about 1860. It is a rather curious fact that its im-
portance was at first unnoticed, and the full recognition of its im-
plications, a few of which we shall now examine, is due to the work,
not of Avogadro himself, but of another Italian, Cannizzaro, some
47 years after the hypothesis had been first put forward, and after
Avogadro himself was dead.
Why Avogadro's Law is important
The importance of the law lies in this fairly simple fact,
that, since it asserts that equal volumes of gases contain
equal numbers of molecules, it enables us to change over
directly from a statement about volumes of gases to the same
statement about molecules of gases. Every time we make a
statement about one volume of any gas, we are also making
a statement about a certain number of molecules of it, and
that number, by Avogadro's law, is always the same, no
matter what the gas may be. Consequently, we can change
over at will, in any statement about gases, from volumes to
molecules and vice versa.
This means that by applying the law to volume measurements of
gases, we can probe right to the heart of a chemical reaction, to the
actual molecules themselves. It is an enormous step to change
directly from an experimental statement like:
2 volumes of hydrogen combine with 1 volume of oxygen giving
2 volumes of steam (temperature and pressure constant)
to
2 molecules of hydrogen combine with 1 molecule of oxygen giving
2 molecules of steam.
The second of these two statements goes right to the essentials of
the reaction, to the very molecules themselves. The law is important
because it gives us this power to reveal the molecules themselves at
work in chemical reactions. Note, however, that it applies only to
gases.
Other examples illustrating this important change from volume
measurements to statements about molecules follow overleaf.
98 A NEW CERTIFICATE CHEMISTRY MOLECULAR THEORY 99

Ammonia. By experiment, 2 volumes of ammonia decompose to Avogadro's Law and the molecular weights of gases
1 volume of nitrogen and 3 volumes of hydrogen.
give We have seen, in Chapter 4, that molecular weights are expressed
as the number of times one molecule of the substance is as
heavy as
Applying the Law,
molecule of nitrogen and
one atom of hydrogen. We have also seen, in this chapter, the very
2 molecules of ammonia contain 1
important relation which exists between the number of volumes of
3 molecules of hydrogen.
gases and the number of molecules of gases involved in chemical re-
Hydrogen Chloride. By experiment, 1 volume of hydrogen com- action. It is now necessary to find how the atom and the molecule of
bines with 1 volume of chlorine to give 2 volumes of hydrogen hydrogen are related to one another. This will lead us to a method
chloride. of determining molecular weights.

Applying the Law,

The nature of the hydrogen molecule
1 molecule of hydrogen combines with 1 molecule of chlorine By experimental work which is fully described later (p. 1 12), it has
to give 2 molecules of hydrogen chloride.
been found that (at constant temperature and pressure):
Nitric Oxide. By experiment, 2 volumes of nitric oxide decompose 1 volume of hydrogen combines with 1 volume of chlorine to give

to give 1 volume of nitrogen and 1 volume of oxygen. 2 volumes of hydrogen chloride.

Applying the Law, Applying Avogadro's Law we can say at once:
2 molecules of nitric oxide contain 1 molecule of nitrogen and
1 molecule* of hydrogen combines with 1 molecule of chlorine to
1 molecule of oxygen.
give 2 molecules of hydrogen chloride.
(Temperature and pressure assumed constant throughout)
Now each of the two molecules of hydrogen chloride must
From only a further step to the deduction of
these statements, it is
contain some hydrogen. The least amount of hydrogen
the formula of the gaseous compounds concerned. This step is given
which can be contained in one molecule of hydrogen
in the later part of this chapter, and the formulas of the common chloride is one atom, because the atom of hydrogen is in-
gases are considered in the next. divisible. Consequently, the least amount of hydrogen there
can be in two molecules of hydrogen chloride is 2 atoms of
How Avogadro's Law explains Gay-Lussac's Law hydrogen. But these 2 atoms of hydrogen must have come
Assume throughout the following paragraph that temperature and from the 1 molecule of hydrogen marked*; therefore, a
molecule of hydrogen must contain at least two atoms of
pressure are constant.
hydrogen.
When gases react chemically, the reactionmust take place between
individual molecules of the gases. As Dalton suggested in the similar But hydrochloric acid forms with sodium hydroxide one salt only,
sodium chloride. Two series of salts have never been obtained from
case of combination between atoms, the reactions will take place
hydrochloric acid as they have from, for example, sulphuric acid.
between small whole numbers of molecules of the reactants to pro-
duce small whole numbers of molecules of the products. Thus with sodium hydroxide, sulphuric acid can be made to form
We have seen in the last section that, employing Avogadro's Law, both normal sodium sulphate and acid sodium sulphate. Since the
we can change over directly from statements about molecules to hydrogen of hydrochloric acid cannot be replaced in two stages,
is only one hydrogen atom in the
molecule. But the two
statements about volumes, provided that gases only are concerned. there

Making this change, the last sentence of the last paragraph becomes:
the reactions will take place between small whole numbers of volumes
of the reactants to produce small whole numbers of volumes of the
products (all being gases). This is what Gay-Lussac's Law states.
Hence, Avogadro's Law has enabled us to deduce the experimentally
observed Law of Gay-Lussac.
hydrogen atoms necessary for two molecules of hydrogen chloride
have been obtained from one molecule of hydrogen. Hence the
molecule of hydrogen contains two atoms.
Try to visualise what this means. It means that, in ordinary gaseous
hydrogen, no separate atoms of hydrogen exist. All the particles
consist of two hydrogen atoms, locked in a chemical embrace, and
100 A NEW CERTIFICATE CHEMISTRY MOLECULAR THEORY 101

moving always as a single unit, the molecule. It is as if the hydrogen Note that vapour density can be experimentally determined
atoms are paired off to run a perpetual three-legged race. The mole- because it only involves weighing equal volumes of hydrogen and
cule, consisting oftwo hydrogen atoms, never breaks up, except for the vapour.
The molecular weight of a gas or vapour is expressed in the lorm:
the purpose of engaging in chemical reactions. This fact is expressed
H
by writing the hydrogen molecule as t , which means a single mole- Molecular weight of _ Weight of 1 molecule of the gas or vapour
cule of hydrogen containing two atoms. (2H would mean two separ- a gas or vapour Weight of 1 atom of hydrogen
ate hydrogen atoms.) a simple relation between vapour
We shall now show that there is
By a somewhat similar argument, it can be shown that the mole-
density and molecular weight.
cule of chlorine contains two atoms, and the reaction between
hydrogen and chlorine may be diagrammatical ly expressed
Vapour density of _ Weight of 1 volume of gas or vapour
as:
a gas or vapour Weight of 1 volume of hydrogen
TEMPERATURE AND PRESSURE CONSTANT
Temperature and Pressure constant

ft Applying Avogadro's Law, we can say directly:

ft ft 8 8 ft
Vapour density of _ Weight of 1 molecule of gas or vapour
ft 8
8
ft ft * *,
* a gas or vapour Weight of 1 molecule of hydrogen
ft ft <* ft
_ Weight of 1 molecule of gas or vapour
1 volume volume 2 volumes
6H, + 1 .

"* Weight of 2 atoms of hydrogen

6C1, 12HC1
or in simplest terms, Multiplying both sides by 2:
H, + CI, - 2HC1 2 X (Vapour Weight of 1 m olecule of gas or vapour
Fig. 30. density of a gas = Weight of j atom of hydrogen
Note that equal numbers of molecules of hydrogen, chlorine and or vapour)
hydrogen chloride are contained in equal volumes.
= Molecular weight of the gas or vapour
the molecular weight of a gas or vapour is twice its vapour
It is known, from similar experimental evidence and argument, that /.c,
nitrogen and oxygen also have two atoms per molecule and their density.
molecules are written N s and 2 This is expressed by saying that
Molecular weight from vapour density. Regnault's Method
.

the molecules of hydrogen, chlorine, nitrogen and oxygen are

diatomic or that their atomicity is 2.
Atomicity. The atomicity of an element is
tained in one molecule of the element.
Relation between vapour density and molecular weight
The relative densitiesof solids and liquids are expressed with
We have already noted that to find the vapour density of a gas or
the number of atoms con- vapour it is only necessary to obtain the weight of a certain volume of
the gas or vapour and the weight of an equal volume of hydrogen,
both at the same temperature and pressure.
Unfortunately, direct weighing of hydrogen and other gases in this
way very difficult, partly because the actual weights of convenient
is

reference to water, but it would be most inconvenient to deal with volumes of the gases are small, and partly because changes of tem-
gases in this way because of the great difference between the densities perature, pressure and humidity in the atmosphere introduce errors

of water and gases. during the course of the experiments.

Definition. The vapour density of a gas or vapour is expressed as the In principle it is only necessary to evacuate a globe, weigh it and
fill it with hydrogen and weigh it; then evacuate it again, fill with the
number of times a certain volume of the gas or vapour is as heavy as
the same volume of hydrogen at the same temperature and pressure. gas and weigh again, temperature and pressure remaining constant.
This is known as Regnault's Method. Then,
Expressed in another form, this becomes:
Vapour density of _ Weight of 1 volume of gas or vapour
Vapour density _ (Weight of globe + gas) — (weight of globe)
of the gas ~ (Weight of globe + hydrogen) — (weight of globe)
a gas or vapour We ght of i volume of hydrogen
Molecular weight of the gas = 2 X vapour density.
i

and
Temperature and Pressure constant
102 A NEW CERTIFICATE CHEMISTRY MOLECULAR THEORY 103

A simpler method of finding molecular weight, which can be On this the atomic weight of oxygen was 15.88, or
standard,
applied to the particular case of oxygen, is described in the next
O= atomic weight scale continued in use until the early
15.88. This
section. years of the twentieth century when it was found desirable to make a
Determination of molecular weight of oxygen slight modification by basing the scale on the
standard of O 16. =
This meant multiplying all existing atomic weights by the fraction
This method is simplified by:

1. Weighing the oxygen as a loss in weight of potassium chlorate. J^L so that, for example, the atomic weight of hydrogen was raised
15.88'
2. Using the fact that 1 dm 3 of hydrogen at s.t.p. weighs 0.09 g,
to 1.008.
and measuring the volume of oxygen.
The principal reason for making this change was that many
Weigh a hard glass test-tube containing some potassium chlorate. equivalents of elements (and hence their atomic weights) were
Use apparatus of Fig. 11, p. 46. Fill the siphon tube with water by determined by a direct experimental relation with oxygen. If 1, H=
blowing, with clip open, into the short aspirator tube. Close the clip. hence O=
15.88, was used as standard, any error in the figure 15.88
Attach the hard glass test-tube to the short aspirator tube and put was transferred to the equivalents of these many elements. If, how-
the measuring cylinder into position. Open the clip. (Water will flow ever, the standard was directly O-
16, hence H=
1.008, any error
for a second or two; longer flow indicates leakage which must be in the 1.008 affected hydrogen only. In conformity with this new
corrected.) Heat the potassium chlorate. Oxygen evolved will displace scale, the definition of equivalent of an element (p. 37)
was modified
water into the measuring cylinder. When it is suitably filled, let the to 8 mass units of oxygen exactly and to the corresponding
to relate
apparatus cool. Equalise water-levels in measuring cylinder and figures for the other elements used experimentally.
aspirator (so that oxygen atmospheric pressure). Close the clip,
is at Definition. The gram-equivalent weight of an element is the number of
remove the measuring cylinder and read the volume of water (i.e., grams of the element which combine with or displace 8 grams of
of oxygen). Weigh the hard glass tube and record room temperature oxygen, 1.008 grams of hydrogen or 35.46 grams of chlorine.
This scale continued in use until January 1, 1962, when a new
and pressure. scale

Readings based upon carbon was substituted.

about
Weight of hard glass tube and potassium chlorate 21.32 g
There were two reasons for this change. The first was that,
ordinary atmospheric oxygen is not a uniform
Weight of hard glass tube after heating
1930 it was found that
21.03 g '7
material but contains three isotopes, 8 (99.76%), 8 l
(0.04%) and
O
.". Weight of oxygen = 0.29 g
^O (0.02%). If the atomic weight of oxygen-16 is taken as 16, O=
Volume of oxygen = 217 cm 3 the average atomic weight of atmospheric oxygen is 16.0044. Further,
Temperature = 15°C the isolopic content can vary chemical oxygen does
slightly so that
Pressure (corrected for vapour pressure of water) = 750 mm not provide a constant standard. The second reason
for the change
773 7Sfl was by the 1950's, the principal
Volume of gas = 217 x =^ i£ cm to carbon as reference element that,
at s.t.p. x 3
means for atomic weight determination had become the mass
spectro-
288 760
oxygen.
= 203 cm s meter to which carbon is much more suited than
after international consultations between
chemists and physi-
029 * 100° So,
.'. 1000 cm3 of oxygen weigh g = 1.43 g at s.t.p. cists in 1960-1, it was agreed to adopt an atomic weight scale based
upon the carbon isotope,
«
*C, as C-
12. (This isotope is usually
But 1000 cm 3 of hydrogen at s.t.p. weighs 0.09 g referred to as carbon-12 or
,2
C.) The numerical effect on atomic
parts per million
/. Vapour density of oxygen = -^— = 15.9
weights was only slight— a reduction of about 37
(e.g., O-16.0000, became O 15.9994). -The chemical atomic
small proportion
.\ Molecular weight of oxygen = 15.9 X 2 = 31.8 weight of carbon is not exactly 12; the presence of a
l3
C, raises it to 12.01115, with an error of ±0-0°™»
Scales of atomic weight of the isotope,
isotopic composition. The reference standard
because of variation in
It was stated in Chapter 4 that, after the mid-nineteenth century, carbon (since the valency
for equivalents must now be 3 mass units of
the atomic weight scale was based on the reference standard, 1. H= of carbon is 4) but the former reference standards of 8
units of oxygen,
 :

104 A NEW CERTIFICATE CHEMISTRY MOLECULAR THEORY 105

1.008 units of hydrogen and 35.46 units of chlorine remain numeri-
cally unaffected at the ordinary standards of experimental accuracy.
22.4 dm3 at s.t.p. This volume is called the molar volume (or gram-
molecular volume) of the gas.
Definition. The molar volume (or gram-molecular volume, G.M.V.) of
Molar volume (or gram-molecular volume) of hydrogen
any gas is the volume occupied at s.t.p. by one mole of molecules (gram-
molecule) of the gas and is 22.4 dm
3
It was shown on p. 99 that the hydrogen molecule is diatomic and .

result because it means that if

is written as H2
Expressing . this on the standard of ia C = 12 and This is a most important and useful
H= 1.008, we have: we write the molecular formula of any gas and refer it to grams as
weight-units, the volume of gas indicated is always 22.4 dm at s.t.p.
3
H,
Thus:
2 X 1.008
or 2.016 H2 O, N 2 C0 2 H 2S SO s
CI*
If this is expressed in the scientific weight unit (gram), it becomes 2.016 32 28 44 34 64 71 grams
2.016 g and this is called one mole of molecules of the gas (or one 22.4 22.4 22.4 22.4 22.4 22.4 22.4 dm 3 at s.t.p.
gram-molecule of it). It contains the Avogadro Constant (or Number)
of molecules, 6.02 x 10 23 . This means that the gases all have differing densities except where, by
coincidence, their molecular weights are the same, e.g., CO» and
Definition. The molar weight (or gram-molecular weight, G.M.W.) of
any gas is its molecular weight expressed in grams. NA 44.

We now have Application of molar (gram-molecular) volume of gases to determina-

H, tion of molecular weights
Molar weight 2.016 g (or G.M.W.) molecular
It follows from the above result that, to determine the
By experiment, it has been found that 1 dm 3 of hydrogen at s.t.p. weight of a gas in grams, we have simply to find the weight of the gas
in grams which occupies 22.4 dm at s.t.p.
3
2.016
weighs 0.09 g. Therefore, 2.016 g of hydrogen occupy dm 8 , or
0.09 Example. 350 cm 3 of a certain gas were found to weigh 1 g at s.t.p.
22.4 dm 3
, at s.t.p. This volume is called the molar volume (or gram- conditions. What is the molecular weight of the gas?
molecular volume) of hydrogen. dm3 (or 22 400 cm3) of the
From the data given, the weight of 22.4
We
formula,
see,
H
from
s,
this, that if we use grams as our weight-unit, the
may denote either 2.016 g of hydrogen or 22.4 dm3 of it gas at s.t.p. is
I
—
x 22400 grams or 64 grams.

We have connected the molecular formula of hydrogen with

at s.t.p. Therefore, the molecular weight of the gas is 64. This method of
a volume, rather a convenient result because hydrogen, a gas, is calculation is alternative to the vapour density method given on
usually measured experimentally as a volume. p. 101.

Application of molar (gram-molecular) volume to gas calculations

Molar volumes (or gram-molecular volumes) of other gases

Consider the same volume, 22.4 dm 3 at s.t.p., of some other gas, Example 1. Calculate the volume of oxygen at 12°C and 745 mm
pressure which could be obtained by heating 5 g of potassium chlorate.
say oxygen. Since we are considering the same volume of both oxygen
and hydrogen in the same conditions, we know, by Avogadro's Law, (K =
39; CI 35.5; = 0=16.
Molar, or gram-molecular, volume of
gases at s.t.p. is 22.4 dm*.)
that we must be considering the same number of molecules of the two
gases. But we started from one mole of molecules of hydrogen; there- Calculation. The first requirement is the equation:
fore, the 22.4 dm 3 at s.t.p. must represent the same number of mole- 2KC10 3 -* 2K.C1 + 30 8
cules of oxygen, one mole of molecules (or one gram-molecule)
i.e.,
Note that, in the question, a weight of potassium chlorate is given and
of it. The same argument will apply to any other gas, which gives us a volume of oxygen is wanted. Therefore, in the equation, we insert
this very important result: the weights appropriate to potassium chlorate and the volume appro-
One mole of molecules (or one gram-molecule) of any gas occupies
priate to oxygen. It is quite unnecessary to insert a weight of oxygen.
 :

106 A NEW CERTIFICATE CHEMISTRY MOLECULAR THEORY 107

Using grams as the weight units for potassium chlorate, O, (one Converting this volume to 14°C and 770 mm as the example
mole, or gram-molecule, of oxygen) represents 22.4 dm 3 at s.t.p.; requires:
30 a represents, therefore, 3 x 22.4 dm 3 or 67.2 dm».
Inserting weights and volume, we have:
,
PlVl = PjP*
2KC10 8 -> 2KC1 + 30 8 760 x 0.677 770 X P,
2(39 + 35.5 + 48) g 67.2 dm 3 273 287
245 g at s.t.p.
760 X 0.677 X 287
From the equation: Of = dm3
273 X 770
245 g of potassium chlorate yield 67.2 dm 3 of oxygen,
= 0.703 dm 3
so 5 g of potassium chlorate yield — '
_
* - dm3 of oxygen, Avogadro Constant
3
= 1.37 dm 3
of oxygen at s.t.p.
The Avogadro constant has the value, 6.02 X 10* and is defined
as the number of atoms in exactly 12 g of
carbon-12. It is often
Converting this volume to 12°C and 745 mm pressure as the example called the Avogadro number. It is also the number of molecules
requires:
contained in one mole of molecules of any gas. It is, for example,
Pi»i _ Pi"i the number of molecules contained in 36.5 g of hydrogen
chloride,

ft
r, 32 g of oxygen or 64 g of sulphur dioxide, these figures being the
contains
molecular weights of the gases. The volume of gas which
760 X 1.37 745 X vt
number of molecules always occupies 22.4 dm at s.t.p.
3
this
273 285 atoms contained
The Avogadro number is also the number of in

760 x 1.37 X 285 22.99 g of sodium or 26.98 g

"» = dm 3 a mole of atoms of any
being
element, e.g., in
the atomic weights of the elements.
273 x 745 of aluminium, the figures
An name a mole of atoms was one gram-atom, i.e., the
= 1.46 dm* older for
atomic weight of the element in grams. The Avogadro number
of
Example 2. Calculate the volume of hydrogen sulphide at 14° and C electrons is also called a mole of electrons and can liberate in electro-

110 mm pressure which will react with 10 g of lead(IT) nitrate. lysis one mole of atoms of any univalent
metal.
(Pb = 207; N = 14; O= 16. Molar, or gram-molecular, volume of An early method for the determination of the Avogadro number
Millikan, who deter-
gases is 22.4 dm 3 at s.t.p.) (1912) came out of the work of an American,
10~ 19
mined the charge on the electron as 1.59 x coulomb. Since
Calculation. We require first the equation; the nitrate is given as a
96 500 coulombs of electricity were known to liberate one gram-atom
weight so we insert weights under its formula, while the hydrogen
of any univalent element in electrolysis (e.g., 1.008 g of hydrogen),
sulphide is required as a volume so the volume appropriate to one
mole of gas is put under its formula. 1023
X
number of atoms involved must be ^_ u or 6.07
- .
the
H t S + Pb(NO,), ->-PbS + 2HNO a

22.4 dm 3 (207 + 28 + 96) g As stated above, the accepted value today is 6.02 x 1018 (accurate
at s.t.p. 331 g to 3 sig. fig.).

From the equation

Empirical and molecular formula;
331 g of the nitrate react with 22.4 dm 3 of hydrogen sulphide,
A method was given on p. 56 for the calculation of a formula for a com-
so 10 g of the nitrate react with — 4 x 10
22 '-——
dm 3
of hydrogen pound from its percentage composition by weight. It is quite possible
two different compounds to have the same percentage composition by
for

weight either because the compounds have different arrangements of the

sulphide at s.t.p. = 0.677 dm 3
at s.t.p. same atoms inside the molecule, or because the molecular formula of one
 108 A NEW CERTIFICATE CHEMISTRY MOLECULAR THEORY 109

is a multiple of that of the other. Considering the second of these possi- The empirical formula is CH,
bilities, it is clear that acetylene, C
a H„ and benzene, C,H 6 both having
,

92.3% of carbon, will both appear to have the same formula, when the .-. The molecular formula is CH,,, where n is a whole number,
calculation of p. 56 is applied. Thus: the molecular weight is (12/i + 3/i).
.-.

weighs 1.35
From the problem, 1 dm 3 of the compound at s.t.p. g.

. . 1.35 x 22.4
— ,«,„
=30.2
Carbon Hydrogen .-. 22.4 dm s
of the compound at s.t.p. weigh j g

12n + 3/» = 30.2

Per cent by weight 92.3 7.7 =
I5« 30.2
Number of atoms is represented by
n = 2
12 '•' C,H, (ethane)
.-. Molecular formula is

Dividing by smallest ^ =1
7
7.7
Application of Avogadro's Law to determination of atomic weights

The formula appearsto be CH

for both. The reason is that this cal- We have seen in Chapter 4 the great difficulty encountered, in the first

culation always yields the simplest formula which expresses the com- half of the nineteenth century, in the determination of
atomic weights and
position of the substance by weight. Since the ratio of carbon atoms to how the difficulty was overcome in the case of metals by the use of equiva-
hydrogen atoms is the same in CH, QH,
and C,H„ the same composition lent and valency. development from Avogadro's Law, which we are
A
by weight is expressed in all three. This simplest formula which expresses now to consider, supplied a method of determination of the atomic weight
the composition of a compound by weight is called its empirical formula. of non-metals of a certain type.
Thus, the empirical formula of both benzene and acetylene is CH. The most convenient case for us to consider is that of carbon. Suppose
Clearly we must devise a method of finding the true or molecular we take the symbol X to denote the atomic weight of carbon. In a molecule
formula of the compounds. This is simple enough. If the true formula is of a carbon compound, there cannot be less than one atom of carbon,
carbon
CH, the molecular weight is (12 + l)or 13;ifC,H„26;irc,H„78,andso and there may be two, three, four or any small whole number of
on. Thus, a determination of molecular weight will at once decide the atoms. This means that, in the molecular weight of a carbon
compound,
true
formula, and, in practice, this means determining the vapour density there must be X, 2X, 3X or n units of weight of carbon (n is a small whole
X
(p. 101) of the compound. The vapour density of acetylene is 13, and of number). ,
benzene 39; that is, their molecular weights are 26 and 78 respectively. The molecular weight of any carbon compound can be found by deter-
the
mining first its vapour density (by the method on p. 101, provided
This gives a molecular formula C,Ha for acetylene and that
QH,
for benzene.
analysed and the
compound is gaseous). The compound can then be
Definitions.The empirical formula of a compound is the simplest
percentage of weight of carbon in it determined. The weight of carbon
in
formula which expresses its composition by weight.
the molecular weight is then given by the expression.
The molecular formula of a compound is one which expresses the Percentage of carbon Mol ecular weight of compound
actual number of each kind of atom present in its molecule. 1
TOO
Another example will illustrate the point further. If this is
compounds, the results must represent
applied to several carbon
In the table
A
gaseous compound of carbon and hydrogen contains 80% carbon by the weights of the number of carbon atoms in the molecules.
weight. One dm' of the compound at s.t.p. weighs \.35g. Find its on p. 110, the figures are given for several compounds.
formula. (C = 12; H molecular
- 1. G.M.V. of any gas is 22.4 dm* at s.t.p.) The figures in the last column correspond to the presence or one, two,
others are
three or more carbon atoms. The lowest weight is 12 and the
in our list any
multiples of 12. Now it is obvious that, if we have included
compound containing only one carbon atom per molecule, that com-
pound will be the first, methane, or the last, formaldehyde, because in these
the weight of carbon is the least. If, therefore, the
molecules of methane
Per cent by weight atomic
and formaldehyde do actually contain only one carbon atom, the
large
Number of atoms is represented by weight of carbon is 12. This process has been applied to a very
number of carbon compounds, and the weight of carbon in the molecular
weight has always been found to be 12, or a multiple of 12, but never
less.
Divide by smallest
From this we conclude that the least weight of carbon there can ever be in
this weight
the molecular weight of one of its compounds is 12, that
weight
corresponds to the presence of one carbon atom and that the atomic
of carbon is 12.
 110 A NEW CERTIFICATE CHEMISTRY QUESTIONS 111
The method can be applied to determine the atomic weight of any dioxide with excess of concen-
8. By heating a certain weight of lead
clement forming a large number of gaseous or easily volatile compounds. measured at
trated hydrochloric acid, 743 cm of chlorine were obtained,
3

27°C and 755 mm. Calculate the weight of lead dioxide used and find
the weight of lead chloride which was produced during
the reaction.
Compound
Vapour Molecular % of carbon Weight of carbon
the term 'molecular weight'. Give a short account
density by weight by (weight by in the molecular 9. Explain carefully
experiment (-2XVD.) experiment) weight of the experiments and reasoning which lead to the conclusion
that the
molecular weight of steam is 18. (O. and C.)
10. Define the terms 'vapour density* and
'molecular weight', and
Methane 8 16 75.0 75 x
j£ = i2 deduce from your definition the relation that exists between them, stating
any assumption that you make in the deduction. A metallic
chloride has a
Ethane 15 30 80.0 80 x-^24 vapour density of 130 and contains 54.6% of chlorine by weight. How
many atoms of chlorine does its molecule contain? (CI = 35.5.) (C.)
Propane 22 44 81.8 81.8 x « - 36 1 1. What is the relation between molecular weight and vapour density,
and how do you account for it?
At atmospheric pressure and 546°C, 50 cm of phosphorus 3vapour weigh
3

85.7x^ = 0.093 g. What is the molecular weight of phosphorus (1 dm of

Ethylene 14 28 85.7 24 hydrogen
at s.t.p. weighs 0.09 g)? (O. and C.)
12. Explain how Avogadro's Law can be used to
establish (a) molecular
Acetylene 13 26 92.3 92.3x^=24 oxygen
weights; (o) atomic weights. Illustrate your answer by reference to
and carbon. (O. and C.)
Formaldehyde 15 30 40.0 40 »*-« 13. A flask of about 500 cm capacity, fitted with
3 a rubber stopper,
weighed 90.512 g when filled with air. Hydrogen chloride from a generator
was passed in for a few minutes, the stopper was replaced, and the flask
and its contents now weighed 90.660 g.
QUESTIONS The flask was inverted in a trough of water, the stopper was removed
under water, and eventually 456 cm of liquid entered when the levels had
3

All necessary atomic weights may be found on been adjusted. Given that the temperature of the gases was 13 C and that
p. 532.
the atmospheric pressure was 770 mm of mercury, find:
1. What the weight of 22.4 dm 3 (gram-molecular volume) of the
is
(a) The weight of a litre of hydrogen chloride at s.t.p.
following gases at s.t.p. (a) ammonia; (6) hydrogen sulphide; (c) nitro-
1
(£) The molecular weight of hydrogen
chloride from the given data.
gen; (a ) chlorine; (e) dinitrogen oxide?
(One dm 3 of hydrogen at s.t.p. weighs 0.09 g, one dm of air at
3

2. Calculate the molecular weights of the following gases from the state- s.t.p. weighs 1.293 g.) (B.)
ments:
14. Explain the use of a chemical equation and the information which
(a) 0.8 g of oxygen occupied at s.t.p. a volume of 560 cm*. itconveys.
exact
(b) 1400 cm' of sulphur dioxide measured at s.t.p. weighed 4 g. Give equations representing three chemical reactions and state the
(c) 1.12 dm' of nitrogen monoxide measured at s.t.p. weighed 1.5 meaning of each equation. (O. and C.)
g.
3. What volume of carbon dioxide at s.t.p. could be obtained by 15. Describe in detail the qualitative and quantitative
experiments you
dissolving 1 50 g of pure marble (calcium carbonate) in dilute nitric acid
? would carry out to show that the equation CuO + H, = aHO+ Cu re-
4. 1 1 6 g of magnesium was allowed to react with excess dilute sulphuric
. presents the action of hydrogen on red-hot copper oxide. (O.)
acid. What volume of hydrogen measured at s.t.p. was liberated?
5. An evacuated flask weighed 20.70 g. Filled with dry hydrogen, it was
found to weigh 20.94 g. Filled with dry chlorine at the same temperature
and pressure as the hydrogen, the flask weighed 29.22 g. Using these data
alone, find the molecular weight of chlorine.
6. 1 dm* of ozone measured at 20°C and 750 mm
was converted into
oxygen by heating. If the resulting oxygen was measured at 30°C and
750 mm, what volume would it occupy?
7. 100 cm' of hydrogen were sparked with 30 cm' of oxygen, both
gases
at 1 10°C and 760 mm. What is the total volume of gas left after cooling
to
the original temperature and pressure? What percentage of this gas
by
volume is steam?
 AMMONIA 113

mixed gases to pass for 5 to 10 minutes. Close both taps. Attach

wires from a coil, and arrange a plate of thick glass between the tube
and the observers. Close the circuit and a flash is seen but no sound
is heard. Note that the green
colour of chlorine has now disappeared.
Chapter 10 Fill the tube leading to one tap
with mercury, and, holding the
under mercury in a mortar.
liquid in place with the finger, invert

Open the tap. No gas enters or leaves. Close the tap, replace the
mercury in the tube by water, and open under the surface of water.
Formula of Gases The and almost fills the tube.
latter rises
Note. The experiment on page 142 (Electrolysis of hydrochloric
acid) shows that the gases which fill the eudiometer tube consist of
It isimportant to mention the conditions of temperature equal volumes of hydrogen and chlorine.
This proves that the whole of the gas in the tube was
hydrogen
and pressure whenever gas volumes are measured
because any excess of hydrogen or chlorine would not have
chloride
TN this chapter, we
shall give the experimental evidence,
and the dissolved with this rapidity. This experiment proves that, starting
Areasonmg from by which the formula? of a number of common chlorine
with half a tubeful of hydrogen and a half a tubeful of
it,

gases have been established. It is most important combination, a tubeful of hydrogen

that you should (see p. 142), we obtain, by their
note carefully the way in which Avogadro's
Law is continually chloride (temperature and pressure constant) or
employed in establishing these formula;, both directly
in converting
volume measurements into evidence of the numbers 1 volume of hydrogen combines with 1 volume of chlorine to give
of molecules
involved and, indirectly, when vapour 2 volumes of hydrogen chloride (temperature and pressure
density measurements are
employed. The importance of the Law constant).
in thefollowing work cannot
be over-estimated. Applying Avogadro's Law, we may substitute molecules for

volumes, all the substances being gases.

Hydrogen chloride
.-. 1 molecule of hydrogen combines with 1 molecule of chlorine
All volume measurements made during the following
experiment to give 2 molecules of hydrogen chloride.
are under the same conditions of temperature and pressure.
But 1 molecule of hydrogen and 1 molecule of chlorine each con-
tain 2 atoms.
=0< hydrogen
Cone. /. 2 molecules of hydrogen chloride contain 2 atoms of
Hydrochloric and 2 atoms of chlorine
'
Anhydrous acid
Calcium—* .*. 1 molecule of hydrogen chloride contains 1 atom of hydrogen
Chloride ~*v
^
Pot moistened
and 1 atom of chlorine

HC1
with saturated /. The formula of hydrogen chloride is
solution of +.
Calcium Chloride £
__ The equation for the —
above reaction is H 2 + Cl a > 2HC1.
Fig. 31. Note. Since the reactants and products are all gaseous the vapour
The apparatus density is not required.
usually supplied for this experiment (see Fig.
31)
is far too large to be filled in a reasonable
period of time, and is too Ammonia gas
liable to burst. A smaller model
of about 50 cm 3 capacity (obtainable
from manufacturers quite easily) is very suitable The full argument depends upon two experiments (a) and (b).
and the experiment (a) Ammonia gas can be formed by sparking nitrogen and hydro-
can be completely performed in 20 minutes.
Set up the apparatus of Fig. 31 in diffused gen in suitable proportions. This proves that ammonia contains
daylight, and allow the these two elements only. (This experiment is not described here.)
112
114 A NEW CERTIFICATE CHEMISTRY STEAM 115

(b) Hofmann's method (described below) may be used to demon-
strate the volume proportions of the nitrogen and hydrogen combined
in ammonia. The method depends on the following facts:
(i) That ammonia reacts with chlorine, liberating nitrogen and
forming hydrogen chloride,
(ii) That the hydrogen and chlorine combine in equal volumes
when hydrogen chloride is formed. (See last experiment.)
The original volume, AB, of chlorine combined with hydrogen
from the ammonia to form hydrogen chloride. A volume, AB, of
hydrogen from the ammonia must have been used up to combine
with this chlorine (see [ii] p. 1 14). At the same time, one-third of a
volume AB of nitrogen was liberated from the ammonia.
*. 3 volumes of hydrogen were combined with 1 volume of
ammonia gas (temperature and pressure constant).
nitrogen in

Take an apparatus similar to that of Fig. 32. It can easily be made Applying Avogadro's Law, we may replace 'volumes' by 'mole-
by heating a burette (a damaged one will be quite satisfactory if the cules'.
length from the tap to the open end is 40 cm or more) and drawing
.*. 3 molecules of hydrogen combine with 1 molecule of nitrogen
out the heated portion until it forms a
constriction of which the diameter is .*, 6 atoms of hydrogen combine with 2 atoms of nitrogen or,
VC about that of ordinary glass-tubing, and
in the simplest terms,
then making a file-scratch on the con-
A striction and breaking AB separate from 3 atoms of hydrogen combine with atom of nitrogen
1

C. AB should be about 30 cm long .*. the simplest (empirical) formula for ammonia gas is NH 3 and
and graduated into three equal portions. its molecular formula is (NH 3 )« where n is a whole number
Attach AB to a chlorine generator 1 in a
,'. the molecular weight of ammonia gas is (14 + 3)/i or 17n.
fume-chamber and fill it with chlorine.
Add the rubber-tubing and clip, and the We now need the molecular weight of ammonia gas to find the
portion C, and clamp the whole appa- value of n.

ratus in a vertical position. Put a little

The vapour density of ammonia gas is 8.5.
Water concentrated ammonia into C, cautiously
release the clip and allow a little of the .', its molecular weight is 17

8
ii ammonia
flash
to enter AB. There will be a
of light and white fumes of ammo-
/.

/.
17n =
n=
17
1

Fig. 32. nium chloride will appear. Carefully allow

Formula of ammonia. more ammonia to enter AB until there
.*. the molecular formula of ammonia gas is NH 3

is no further reaction and a few drops Equations

of liquid have collected at B. Then put dilute sulphuric acid into 2NH 3 + 3C1 2 ->Nj-f-6HCl
C, colour it with a little litmus solution and run it into AB to
neutralise the excess ammonia, taking care that C does not become
Then 6HC1 + 6NH -> 6NH„Cl 3

empty of liquid or air will be drawn into AB. When the solution in
AB is red (i.e., when all the ammonia has been neutralised) remove
C and place AB in a wide, deep vessel filled with water so that
the tap B is well immersed. Open the tap. Water will enter. Push
AB down into the vessel until the levels of water inside and out-
side are equal, so giving atmospheric pressure inside AB. It will then
be found that the gas left occupies one-third of the volume of AB.
The gas is nitrogen.
To teachers. It is convenient lo make this apparatus part of the delivery-tube
1
when chlorine is being prepared as a demonstration experiment. The tube is
then automatically filled with chlorine without extra trouble.
Adding 8NH 3 + 3C1, -*• N 2 + 6NH 4C1.
Steam
The apparatus (see Fig. 33) consists of a stout eudiometer tube
surrounded by a jacket which contains a vapour at 130°C (amyl
alcohol boils at 130"C at 760 mm
pressure). The other limb of the
eudiometer tube serves as a manometer, for mercury can be run
into and out of this tube, so altering the pressure. One volume of
oxygen is introduced and then two volumes of hydrogen. The open
end of the tube is suitably plugged so that the mercury is not blown
out. The mixture is exploded by means of an electrical spark and the
116 A NEW CERTIFICATE CHEMISTRY NITROGEN MONOXIDE 117
plug is removed. On allowing the gas to cool down to 130°C and
That is, 1 volume of nitrogen is contained in 2 volumes of nitrogen
equalising the mercury levels in the two tubes it is found that there
monoxide (temperature and pressure constant).
are two volumes of steam left in the tube. (All the above measure-
Using Avogadro's Law, we may substitute 'molecules' for
ments of volume are made at laboratory pressure and 130°C.) On 'volumes'.
cooling the apparatus below 100°C the steam condenses to water
and the mercury rises to the top of the enclosed tube showing that
all the oxygen and hydrogen have been used up since they would not

condense to a liquid as does the steam.

From this experiment Hard glass tubs

7b Induction
coil
Vapour of 2 volumes of hydrogen and 1
Amy/ Alcohol Iron wire
aCB.P.I3Q'C volume of oxygen form 2 vol-
umes of steam.
Applying Avogadro's Law we may
substitute molecules for volumes, all
Steam
the substances (at this temperature) Mortar
Htrcury being gaseous.

.*. 2 molecules of hydrogen and

1 molecule of oxygen form 2

molecules of steam
ssriw
.'. 1 molecule of hydrogen and \
molecule of oxygen form 1
Fl0, "• Fig. 34.
molecule of steam
Volume composition of steam. Volume composition of oxides of nitrogen.
But the molecule of hydrogen con-
tains two atoms and the molecule of oxygen contains two atoms. .'. 1 molecule of nitrogen is contained in 2 molecules of nitrogen
.*. Formula for steam is H2 monoxide
Note. Since the reactants and the products are allgaseous under the .'. 2 atoms of nitrogen are contained in 2 molecules of nitrogen
conditions of the experiment the vapour density is not required. monoxide
,\ 1 atom of nitrogen is contained in 1 molecule of nitrogen
Nitrogen monoxide
monoxide
A suitable volume of nitrogen monoxide is measured at atmos- /. the formula of nitrogen monoxide is NO* where x is a whole
pheric pressure (levels A and B equal) in the hard-glass tube (Fig. 34). number
The spiral of iron wire is then electrically heated to red heat. The
.'. the molecular weight of nitrogen monoxide is (14 -j- 16x).
metal combines with the oxygen of the nitrogen monoxide liberating
nitrogen (the residual gas can be shown to be inactive). After about The vapour density of nitrogen monoxide is 15.
20 minutes the switched off and the tube allowed
electrical current is
The molecular weight of nitrogen monoxide is 30.
to cool. Water-level A
rises towards C.
= 30
After the tube has been transferred to a deep vessel and lowered
.-. 14 + 16x
until the levels C and B are equal, the volume of nitrogen is measured
x= 1

and is found to be one-half of the original volume of nitrogen mon- .". formula of nitrogen monoxide is NO
oxide. 3Fe + 4NO -»• Fe 8 4 + 2N,
118 A NEW CERTIFICATE CHEMISTRY CARBON DIOXIDE 119

Note. Pure nitrogen monoxide for this experiment is conveniently Applying Avogadro's Law, we may substitute
prepared by half-filling a small flask with iron(II) sulplmte crystals,
covering them with dilute sulphuric acid, warming and dropping
w. Platinum
'molecules' for 'volumes'.

wires
sodium nitrite solution into the mixture from a tap-funnel. .". 1 molecule of hydrogen is contained in 1

molecule of hydrogen sulphide

Dinitrogen oxide Hydrogen .". 2 atoms of hydrogen are contained in 1
Sulphide.
Exactly the same experiment is performed as for nitrogen monoxide molecule of hydrogen sulphide
except that the gas must be confined over mercury because dinitrogen

r the formula of hydrogen sulphide is rlgS*,

.".

oxide is fairly soluble in water. The hard-glass tube should be only Mercury
where at is a whole number
about half-filled with the gas at first. It is found that the volume of
nitrogen left is equal to the volume of dinitrogen oxide taken.
,*. the molecular weight of the gas is (2 + 32x).
Fia. 35.
.". 1 volume of nitrogen is contained in 1 volume of dinitrogen The vapour density of hydrogen sulphide is 17.
Volume composi-
oxide (temperature and pressure constant). tion of hydrogen .'. The molecular weight of hydrogen sulphide
sulphide.
is 34.
Using Avogadro's Law, we may substitute 'molecules' for
'volumes'. /. 2 + 32x = 34
.'. 1 molecule of nitrogen is contained in 1 molecule of dinitrogen x= 1

oxide .". the formula of hydrogen sulphide is H gS

.". 2 atoms of nitrogen are contained in 1 molecule of dinitrogen H 2 S-»-H + 2 S
oxide
Carbon dioxide
.". the formula of dinitrogen oxide is N sOa (* is a whole number) The apparatus of Fig. 36 is used. A little dry powdered graphite
.'. the molecular weight of dinitrogen oxide is (28 + 16x). (0.02g is cm 3
placed in the dry tube, and dry
required for 40 ) is

oxygen is passed through the whole apparatus for 3-4 minutes. The
The vapour density of dinitrogen oxide is 22
clip is closed and mercury poured into the manometer. The clip is
,*. Molecular weight of dinitrogen oxide is 44. momentarily released to make the pressure in the tube atmospheric.
.*. 28 + \6x = 44 The graphite is heated with a small flame, and it burns (not always

:.x= l
obviously) to carbon dioxide. Expansion causes the level at to fall, C
.*. the formula of dinitrogen oxide is N and the level at D
to rise, 1 but, when the bulk has cooled, the levels
2
at C and D
return to their original positions, that is, the volume of
3Fe + 4N 2 -* Fe 3 4 + 4N„ carbon dioxide formed is equal to the volume of oxygen used.
.'. 1 volume of oxygen is contained in 1 volume of carbon dioxide
Hydrogen sulphide
(temperature and pressure constant).
A convenient volume of hydrogen sulphide is confined over mer- Applying Avogadro's Law, we may substitute 'molecules' for
cury at atmospheric pressure (Fig. 35). By means of an induction
'volumes'.
coil, electric sparks are passed between the platinum wires for some
time. This decomposes the hydrogen sulphide into its elements.
.". 1 molecule of oxygen is contained in 1 molecule of carbon
Solid sulphur (of negligible volume) is deposited and hydrogen is dioxide
left. It is found that, when the tube has cooled, the volume of hydro- .*. 2 atoms of oxygen are contained in 1 molecule of carbon dioxide
gen left is exactly equal to the volume of hydrogen sulphide taken .'. its formula is C„O s
(temperature and pressure constant).
.'. its molecular weight is 12* + 32.
.". 1 volume of hydrogen is contained in 1 volume of hydrogen danger of being remove the
* If the level at C falls so that gas is in lost,
sulphide (temperature and pressure constant). burner and close the mouth of tube D lightly with the finger.
120 A NEW CERTIFICATE CHEMISTRY CARBON MONOXIDE 121

The vapour density of carbon dioxide is 22.

2. Another 200 cm
3
of the same sample of ozonised oxygen is
.". The molecular weight of carbon dioxide is 44. heated, converting the ozone to oxygen. It will be found that there is
3
/. 12* + 32 = 44 an increase in volume of x/2 cm on cooling to the original tempera-
ture, pressure remaining constant. This means that the oxygen formed
x = 1
from the ozone occupies the x cm formerly occupied by the ozone,
3

.'. the formula of carbon dioxide is CO a 3x

— cm 3
together with a further x/2 cm3 , i.e., in all.
C + o -> C0 2 3

rXo .-. x cm 3 of ozone yield — cm 3

oxygen at same temperature and

pressure.

Or 2 volumes of ozone yield 3 volumes oxygen at same temperature

Dry Carbon
and pressure.
WltZA
.*. By Avogadro's Law,
Oxygen
aqm 2 molecules of ozone yield 3 molecules of oxygen,

i.e., 20„ = 30,

.-. n =3
Mercury
and the formula of ozone is O s

Carbon monoxide
A measured volume of carbon monoxide, confined over mercury in a
Fig. 36. eudiometer tube, is mixed with a measured volume of oxygen equal to
Formula of carbon dioxide. several times its own volume. The mixture is exploded by a spark passed
between platinum leads sealed through the glass. After cooling, the volume
of residual gas is measured and the carbon dioxide is absorbed by allowing
some concentrated caustic potash solution to rise above the mercury. (The
potash solution is introduced at the bottom of the tube by means of a small
Sulphur dioxide pipette bent at the tip.) The diminution in volume caused by the potash
represents the volume of carbon dioxide formed. The residual volume is
The same experimental work is carried out as for carbon dioxide, the excess oxygen, and, by subtracting this from the original volume of
substituting sulphur for carbon. As in the case of the carbon dioxide oxygen taken, the volume of oxygen used up is obtained. (All measurements
the volume of sulphur dioxide formed is equal to the volume of are taken at room temperature and atmospheric pressure.)
It will be found that
oxygen used.
2 volumes of carbon monoxide combine with 1 volume of oxygen to form 2
The reasoning to obtain the formula, S0 2 is the same as for ,
volumes of carbon dioxide.
carbon dioxide, using the vapour density of sulphur dioxide, 32, Using Avogadro's Law, we may substitute 'molecules' for 'volumes'.
and the atomic weight of sulphur, S = 32. Then, 2 molecules of carbon monoxide combine with 1 molecule of oxygen
to form 2 molecules of carbon dioxide.
Ozone .". 1 molecule of carbon monoxide contains \ molecule less oxygen than
Ozone can be made from oxygen and can be converted by heat one molecule of carbon dioxide
into oxygen and no other product. It must therefore have the formula, .*. 1 molecule of carbon monoxide contains one atom of oxygen less

On The value of n is established as follows:

. than one molecule of carbon dioxide
1. Ozone reacts with turpentine. Suppose on treatment with tur- But the formula of carbon dioxide is COj
pentine, 200 cm 3 of ozonised oxygen shrink in volume by x cm 3 . .'. the formula for carbon monoxide is CO.
This means that in the 200 cm 3 of ozonised oxygen there are x cm 3 of Note. Since the reaclants and products are all gaseous the vapour density
ozone. is not required.
122 A NEW CERTIFICATE CHEMISTRY

QUESTIONS
1. How would you show experimentally that two volumes of hydrogen
combine with one volume of oxygen to yield two volumes of steam? What
deductions can be drawn from these facts as to the number of atoms in the
oxygen molecule? (C.) Chapter 1
2. Complete the following statements:
(a) Two volumes of hydrogen unite with volume(s) of oxygen to
give volume(s) of steam, all the substances being at 100°C and
atmosphere pressure.
(b) Two volumes of hydrogen unite with volume(s) of nitrogen to Volumetric Analysis
give volumes) of ammonia, all the gases being at the same
temperature and pressure.
State the law which these statements illustrate, and give the name of its
author. The volume employed for solutions in this section
units
how the formula; of steam and ammonia follow from
Explain clearly
the statements you have made. (N.U.J.B.) are the cubic decimetre(dm 3 ) and the cubic centimetre (cm3).
3. Describe two experiments from the results of which the formula CO,
They are respectively equivalent to the litre (1) and millililre
for carbon dioxide may be derived. Point out clearly what assumptions are (ml), the use of which is discouraged in the S.I. system.
made in the deduction of the formula. (B.)
4. Describe a eudiometer and explain shortly how it is used. Give an VOLUMETRIC analysis is a means of estimating quantities of
account of the experiments by which the formula of ammonia may be certain materials (often acids or alkalis) by an analytical process
shown to be NH,. (L.)
which involves measurement of volumes of solutions, using pipettes,
5. Describe the preparation and principal properties of carbon mon-
burettes and (for approximate measurements) measuring cylinders.
oxide. What is the evidence on which the formula CO is assigned to this
gas? (L.) Weighings may also be involved.
6. Give an account of the experimental evidence on which the accepted Definition. A standard solution is a solution of which the concentration
formula for hydrogen chloride is based. 223 cm 3 of hydrogen chloride and isknown.
250 cm" of gaseous ammonia, both measured at 13°C and 770 mm, were For example, a solution known to contain, say, 12 g of sodium
mixed. Calculate the weight of the solid product. (CI - 35.5, N
= 14.) chloride in one dm 3 of solution is a standard solution.
(L.)
The system now generally approved for volumetric work is based
7. State Gay-Lussac's Law of Gaseous Combination, illustrating your
answer by reference to four examples. upon the molar (M) solution. Such a solution of a given compound
How would you show experimentally that a given volume of hydrogen contains the molecular weight in grams (or one mole) of the com-
sulphide contains twice as much hydrogen as an equal volume of hydrogen pound in one cubic decimetre (dm 3) of the solution.
chloride? (L.) Definition. A molar (M) solution of a compound, X, is one which
contains one mole of the compound in one cubic decimetre (dm3 ) of
the solution.
For example, since QHigO,, =
180, a molar solution of glucose
contains 180 g in 1 dm 3
In the case of strong electrolytes such as
.

sodium chloride or sodium carbonate, which do not exist as mole-

cules to any significant extent in dilute solution, the expression
gram formula weight is often used as equivalent to one mole. For
example, the gram formula weight of NajjCOg is taken as 106 g
(Na 2 C0 3 = 106) and molar sodium carbonate solution contains
106 g of the anhydrous salt in one dm 3 of solution. In fact, the
dissolved salt is almost entirely dissociated into ions (in dilute
solution) in the proportion of 2Na + to C0 3 2_ . Also, with many
salts, hydration of ions occurs in solution.
123
124 A NEW CERTIFICATE CHEMISTRY VOLUMETRIC ANALYSIS 125

Molar solutions of some compounds commonly used in titration usual volume of solution made up in a laboratory experiment is
3
250 cm because this volume allows of three titrations of 25 cm
3
compounds in 1 dm 3 of solution:
contain the following weights of the
each, with a reserve for required washings of pipette and possible
sodium hydroxide, NaOH 40 g
M
titration failures. For 250 cm of 0.1
3 solution, the weight of an-
potassium hydroxide, KOH 56 g
hydrous sodium carbonate required is one-quarter of 10.6 g, or
sulphuric acid, H8 S0 4 98 g
2.65 g.
hydrochloric acid, HC1 36.5 g
Experimental. Put about 8 g of pure sodium hydrogen carbonate
sodium carbonate, Nas.CO a 106 g
into a dry, clean evaporating dish and heat it with stirring for, say,
sodium hydrogen carbonate, NaHCO, 84 g Without
15 minutes. Place it in a desiccator to cool, then weigh it.
The figures quoted arc the gram-molecular weights (gram formula further stirring (to prevent loss of solid), heat the dish again for
weights) of the respective compounds. five minutes or so, cool it in the desiccator and weigh, and so on
Derivative concentrations are also used, e.g., 0.1 M, 0.5 M, 2 M, until two consecutive weighings are the same. Store the dish and pure
and these contain one-tenth of, half of and twice (respectively), the sodium carbonate in the desiccator.
weight of solute present in an equal volume of the corresponding M Weigh a watch-glass (or, better, a stoppered weighing bottle) and
solution. weigh out, on to it, exactly 2.65 g of anhydrous sodium carbonate.
Tap the carbonate into a beaker (with lip) of about 400 cm capacity,
3
It is obvious that some accurately standard solution is required as

containing about 50 cm of hot distilled water. Wash down the

a starting-point for volumetric estimations. Actually few compounds 3

are suitable for the direct preparation of an accurately standard watch-glass (or weighing bottle) with a jet of hot distilled water
solution. Some compounds absorb water from the air and, for this from a wash-bottle and allow the washings to fall into the beaker.
reason, cannot be weighed out accurately without excessively This procedure should wash all the sodium carbonate into the
difficult precautions, e.g., sodium hydroxide, potassium hydroxide beaker. Stir with a glass rod till dissolution of the solid is complete,
and concentrated sulphuric acid. Others react with carbon dioxide then cool the solution to room temperature. Leave the rod standing
of the air, e.g., in the solution.
2NaOH (or 2K.OH) + CO a - Na CO8 s (or K CO + H.O
2 s)
Place a very thin smear of Vaseline under the lip of the beaker
and pour the solution down the glass rod into a measuring flask
Solutions may
contain volatile constituents and be liable to change
(250 the beaker out at least twice with jets of cold dis-
cm 3 ). Wash
slowly concentration during ordinary use, e.g., concentrated
in
tilled water directed round the sides and pour the washings down
hydrochloric acid and ammonia.
the glass rod into the measuring flask. Shake the flask gently. Fill it
A compound which is commonly utilised for the direct preparation
of an accurately standard solution
up with cold distilled water almost to the mark, then add more dis-
is anhydrous sodium carbonate.
tilled water drop by drop from a pipette till the lowest level of the
It is best made from sodium hydrogen carbonate of high purity
meniscus is on the mark when at eye-level (to avoid parallax error).
(which can be bought from chemical suppliers). This is done by
Stopper the measuring flask and shake well. The liquid should then
heating the sodium hydrogen carbonate to constant weight, which
ensures completion of the decomposition:
be exactly 0.1 M sodium carbonate solution.
2NaHCO a -»- Na,CO a + H tO + CO s Preparation of a 0.1 molar solution of sulphuric acid
The anhydrous sodium carbonate so formed is very pure and can This preparation cannot be done directly because concentrated
be used in ordinary weighings with no appreciable change of com- sulphuric acid absorbs water rapidly from the air and is never
position. reliably pure. A
solution is prepared which is a little above 0.1 in M
concentration and it is then standardised and diluted with distilled
Preparation of exactly one-tenth molar (0.1 M) sodium carbonate water to exactly 0.1 M.
solution
A molar solution of sulphuric acid contains 98 g of pure acid in
As stated above, molar sodium carbonate solution contains 106 1 dm , so the 0.1
3
M
acid contains 9.8 g of the acid in 1 dm 3
The
.

g
of solute in 1 dm 3 (since Na a CO
s
=
106). Consequently, a 0.1 M 3
concentrated acid has a density of about 1.8 g/cm , so 9.8 g of it
sodium carbonate solution contains 10.6 g of solute in 1 dm 3 . The occupy about 5.5 cm 3 .
126 A NEW CERTIFICATE CHEMISTRY VOLUMETRIC ANALYSIS 127

Experimental. With great care, because of the dangerously cor- lastdrop.) The flask will then contain exactly 25 cm of 0.1
3
M sodium
rosive nature of the acid, take 5.5-6.0 cm 3 of concentrated sulphuric carbonate solution (with a little distilled water which is of no
acid in a small measuring cylinder; pour it, with stirring, into about account).
100 cm3 of cold distilled water in a beaker (with lip). Pour this Add two drops of methyl orange solution (indicator) to the conical
solution into, say, 700 cm 3 of cold distilled water in a measuring flask. This will turn the alkaline solution yellow. Read and note the
flask of capacity 1000 cm 8 , level of acid in the burette. Run acid into the conical flask 2 or 3
wash out the beaker with cm8 at a time, with shaking, allowing a short drainage time between
cold distilled water twice additions, until the liquid flashes pink. Then add the acid more slowly,
1
— » — and add the washings to the
measuring flask. Then add
eventually drop by drop, until the colour of the liquid is orange {i.e.,
the neutral colour for methyl orange). Slight excess of acid will turn
distilled water approximately it fully pink. Read and note the acid level.
Repeat the titration to
25 cm 3
to the mark on the measuring obtain at least two results which differ by not more than 0.1 cm'.
mark U flask,stopper it and shake
Readings
well. This should give sul-
phuric acid of concentration 25.0 cm8 of 0.1 molar sodium carbonate solution used each time
/ a little above 0.1 M. It is Titration 1 2 3
25 now standardised with the
24.0 23.9 24.0 cm 3
2nd burette reading
0. 1 Msodium carbonate sol-
1st burette reading 0.2 0.3 0.4 cm
8

ution prepared above.

Wash out a burette Acid added 218 216 216 cm 8
(50 cm 3) twice with a few cm8
The can be neglected as a run and the average of
50 cm » £. of the approximately 0.1 M first titration

the other two is 23.6 cm8 .

trial

sulphuric acid and run the

acid out through the tap. Since 25.0 cm8 of the exactly 0.1 M
sodium carbonate solu-
(This leaves the burette wet tion require only 23.6 cm 3 of the acid, the acid must be the more
with the liquid it is to contain concentrated in the proportion of 25.0 : 23.6, i.e., the acid must

and nothing is left to conta- be —- x 0.1 M or 0.106 M. The concentration of acid is 98 X

minate the acid solution when 23.6
the burette is filled.) Fill the 0.106 g/dm 3 , or 10.4 g/dm 8 . To make the acid exactly equal in molar
concentration to the sodium carbonate solution, 23.6 cm of the acid
8
burette 1 cm or so above the

cm 3 mark and run a little must be diluted to 25.0 cm , i.e., 1.4 cm of distilled water must be
3 3

of the acid out through the added to 23.6 cm8 of the acid. If 920 cm 3 of the acid are left, it can
1 4
tap, so bringing the acid level
a little below the cm mark
3
be made exactly 0.1 M by the addition of 920 X -^ cm 8
of distilled
Fio. 37.
Burette and pipette. and
filling the tip of the water, or 55 cm8 . After the addition of this volume of distilled water,
burette with acid. the acid should be shaken and should then be exactly 0.1 M. This
Wash out a pipette (25 cm 3 ) twice with a little of the exactly can be tested by titration of the 0.1 M
sodium carbonate solution,
0.1M sodium carbonate solution. This leaves it wet with the solution when 25.0 cm 3 of the acid should be required to neutralise 25.0 dm8
it is to measure. Draw this solution into the pipette of the carbonate solution.
above the mark
and, with the mark at eye-level, allow the solution to run out very These two standard alkaline and acidic solutions can be used
slowly till the lowest level of the meniscus is on the mark. Then allow to standardise other solutions, e.g., sodium hydroxide, potassium
the liquid to run from the pipette into a conical flask (Fig. 37) which hydroxide, hydrochloric acid, and, by their use, a wide range of
has been washed out with cold distilled water only and touch the tip acid-alkali estimations can be carried out. The following examples
of the pipette on to the surface of the liquid. (Do not blow out the illustrate these estimations.
 NBW CERTIFICATE CHEMISTRY VOLUMBTRIC ANALYSIS 129
128 A
27.5 cm 3 of a solution
3
of sodium hydroxide neutralise 25.0 cm of so 50 cm 3 of M H 2 S0 4 produces 44.8 X — 50
- dm 3 of CO,, or
M hydrochloric acid. Calculate (a) the molarity, (b) the concentra- ILK/U

tion of the sodium hydroxide solution in g/dm 3 . 2.24 dm3 at s.t.p.

The object of the calculation is to fix the molarity and concentra- Converted to 15°C and 770 mm pressure, this volume becomes
tion of the sodium hydroxide
hydrochloric acid; consequently
molecular weight of the acid nor
solution.
we
its
We know
require to
concentration in g/dm8
the molarity of the
know neither
.
the -x£M« or 2.33 dm 3 .

g ofanhydrous sodium carbonate, containing some sodium chlor-

15.0
NaOH + HC1 -^NaCl + HgO
were made up to 250 cm3 of solution and 25.0 cm of
3
ide as impurity,
ldm 3 ofM ldm 3 ofM
40g the solution were titrated by HCI. 24.5 M
cm 3
ofM HCl were required
to neutralise the liquid. Calculate the percentage of sodium chloride in
The equation shows that M sodium hydroxide solution and M hydro- the solid.
chloric acid are equivalent to one another volume for volume. Because this calculation, the equation is required, with the insertion of
For
it requires the smaller volume in the titration, the acid used is the quantity of hydrochloric acid in terms of molarity and of sodium
the
more concentrated (in molar terms) of the two reagents. That is, the
carbonate in grams. Sodium chloride does not react.
sodium hydroxide solution is
25 — ^- M, or 0.909 M. Na,CO s + 2HC1 -> 2NaCl + H,0 + CO a
Since the molecular weight of sodium hydroxide is 40, the solution
106 g 2 dm 3 of M
must contain 0.909 X 40 g/dm s or 36.4 g/dm 3 , .
Wt. of sodium carbonate in 25.0 cm 3 of solution =
50 cm3 of M
sulphuric acid are added to an excess of solid sodium
106 X
24.5
hydrogen carbonate. Calculate (a) the weight of sodium sulpliate pro- t
2000
duced, (b) the volume of carbon dioxide evolved at \5°C and 770 mm =
Wt. of sodium carbonate in 250 cm 3 of solution
pressure. {NOpSOf = 142; the molecular weight in grams of any gas
occupies 22.4 dm3 at s.t.p.)

This calculation requires the equation for the reaction and the
insertion into it of the quantities of the reagents involved in the units Therefore, wt. of sodium chloride in the mixture is

in which they are expressed in the data given. The sodium hydrogen
(15.0 -1 3.0) g, or 2.0 g
carbonate is only vaguely stated as in excess and can be ignored
20
quantitatively. The acid is stated in terms of molarity and is so ex- That is, percentage of sodium chloride = -r^T. x 10°
pressed in the equation. Sodium sulphate is required in grams and
the carbon dioxide in terms of volume. The required reaction state- = 13.3
ment then becomes:
2NaHCO s + H,S0 4 -> Na,S0 4 + 2H 2 + 2CO, Normal Solutions
1 dm3 of M 142 g 2 x 22.4 dm3 at The normality system of concentrations for volumetric analysis,
s.t.p.
which has been in use for many years, is based on the normal (N)
From the equation, solution.
1000 cm 3 ofM HjSO, produces 142 g of sodium sulphate Definition. normal (N) solution of a compound, X, is one which
A
contains the equivalent weight in grams of X
in one litre of solution.
so 50 cm3 of M H S0 produces 142 x —— g of sodium sulphate,
2 4 The terms equivalent and litre have recently been declared scienti-
1UUU
fically obsolete after international discussions but the normality sys-
i.e., 7.1 g tem may continue in use for some time yet.
From the equation, Acids. The gram-equivalent weight of an acid is that weight of the
acid in grams which produces 1.008 grams of hydrogen ion, H .
+
1000 cm 3 of MH t S0 4 produces 44.8 dm 3 of CO, at s.t.p.
130 A NEW CERTIFICATE CHEMISTRY VOLUMETRIC ANALYSIS 131

From the following ionisations: and its concentration in grams /lit re. If 900 ml of the acid remain, how
HC1 ^= H+ +C1- may it be made exactly normal?
Since it needs a smaller volume, the acid is the more concentrated
36.5 g 1.008 g
(in terms of normality) in the ratio
of 25.0 : 24.5, i.e., the acid is
H S0 4 ^
2 2H+ + SO«8 - 25.0/24.5 N, or 1.02 N. Substituting the gram equivalent weight of
98 g 2x 1.008 g
HC1 (36.5 g) for N, the concentration of the acid in
grams/litre is

obvious that the gram-equivalent weight of hydrogen chloride is

it is 1.02 X 36.5 or 37.2.
36.5 g, and of sulphuric acid is 98/2 g, or 49 g. That is, a normal To make the acid exactly normal, it must become equivalent,
is, 0.5 ml
solution of hydrochloric acid contains 36.5 g, and of sulphuric acid volume for volume, to the sodium carbonate solution; that
of distilled water must be added for each 24.5
ml of acid. For 900 ml
of acid in one
49 g, litre.

and carbonates. The gram-equivalent weight of an alkali (or

Alkalis
carbonate) is that weight in grams of the alkali (or carbonate) that
of acid, the volume of distilled water required is 0.5 X —
900
ml, or

reacts with 1.008 g of hydrogen ion. 18 ml. After addition of this water, the mixture
should be shaken.
From the following reactions Since the volume (r) of a solution required for a
given purpose

NaOH (or KOH) + H+ Na + (or K+ + H O

) a decreases in the same ratio as the normality (N) of the solution in-
the product, If X v, is constant. That is, if v , ml
40 g 56 g 1.008 g creases, it follows that

Na^COj + 2H + 2Na + + H tO + C0 8
of a solution of normality, x , are N
neutralised by v 2 ml of a solution

106 g 2 X 1.008 g of normality, Nt ,

it isobvious that the gram-equivalent weight of sodium hydroxide is

40 of potassium hydroxide is 56 g and of Na 2 C0 3 is 106/2 g, or
g, This relation is used in the example below.
{containing some
53 g. That is, a normal solution of sodium hydroxide contains 40 g 14.0 g of a sample of anhydrous sodium carbonate
of the alkali in one litre; for potassium hydroxide, the corresponding sodium sulphate as impurity) was made up to 250 ml of solution. 25.0 ml
weight 56 g and, for sodium carbonate, it is 53 g.
is of this solution required 24.8 ml ofN sulphuric acid for titration. Cal-
present the carbonate.
A 0.1 N
solution of sodium carbonate can be made up accurately culate the percentage of impurity in

as described for the 0.1 M

solution earlier in this chapter. The weight The sodium sulphate impurity does not react with the sulphuric
of sodium carbonate needed for 250 ml of 0.1 N solution is 53 X 0.1 acid. Applying the relation mentioned above,
X 250/1000 g, or 1.325 g. Similarly, an approximately 0.1 N solution 25.0 X iV, = 24.8 X N (where N= 1)
of sulphuric acid can be made up as described earlier and requires
2.8-3.0 ml of concentrated sulphuric acid in one litre. The acid can the normality of the sodium carbonate solution being N t
while the

then be standardised as described for the 0.1 acid. M acid is normal. From this,

The normality system possesses the very useful characteristic that

equal volumes of all normal solutions are chemically equivalent to
^ = |^=0.992
one another. For example, 25.0 ml of N sodium hydroxide solution,
or N
sodium carbonate solution, are exactly neutralised by 25.0 ml That the alkaline solution is 0.992
is N
in sodium carbonate. Sub-

stituting the gram equivalent weight of sodium carbonate (53) for N,

of any strong acid. This situation does not apply to molar solutions.
M the solution contains 0.992 X 53 g/litre, or 52.6 g.
For example 25.0 cm s of sodium hydroxide solution require
M
HC1 but only 12.5 cm8 of M
H,SO«. The monobasic Consequently, the weight of sodium carbonate in 250 ml of solu-
25.0 cm 3 of
tion is 52.6/4 g, or 13.15 g. From this,
and dibasic character of the acids (respectively) accounts for this
difference.
percentage purity of sodium carbonate = -j^— X 100
The following examples illustrate calculations with normal solu- 14.0
tions. = 93.7
25.0 ml of a normal sodium carbonate solution are neutralised by
24.5 ml of dilute hydrochloric acid. Calculate the normality of the acid so, percentage of impurity = 6.3
 132 A NBW CERTIFICATE CHEMISTRY

QUESTIONS
1. 12.5 cm' of 0.5 M
sulphuric acid neutralise 50.0 cm' of a given solu-
tion of sodium hydroxide. What is the molar concentration of the sodium
hydroxide solution?
2. 25.0 cm' of a solution of sulphuric acid required 32.0 cm' of 0.1 M Chapter 12
sodium hydroxide solution for neutralisation. Calculate the concentration
of the acid in g/dm».
3. 25.0 cm' of 0.05 M
sulphuric acid neutralised 35.0 cm' of a potassium
hydroxide solution. What is the concentration of the alkali in terms of Electrochemical Series and Electrolysis
(a) molar concentration, (b) g/dm'?
4. 25.0 cm' of 0.5 M
sulphuric acid arc mixed with 30.0 cm' of M
sodium hydroxide solution. What volume of 0.1 M
sulphuric acid will just
neutralise the excess of alkali? THE ELECTROCHEMICAL SERIES
5. What volumeof a molar solution of sulphuric acid would exactly
Method of obtaining the series
neutralise 25.0 cm* of a sodium hydroxide solution containing 60 g of
the alkali in 1000 cm'? (Na = 23, = 16,O H=
1.) is a well-known fact that certain metals will displace other metals
6. What volume
of 0.1 M
hydrochloric acid would react exactly with
ITfrom solutions of their salts in water. For example, iron will displace
25.0 cm* of a sodium carbonate solution containing 5.20 g of anhydrous
copper from copper sulphate solution, and zinc will displace silver
salt in 1 dm' of solution? (Na,CO, = 106.)
from silver nitrate solution.
7. 25.0 cm* of a solution containing 10.6 g of sodium carbonate in
1000 cm* required 23.0 cm* of hydrochloric acid for neutralisation. Fe -f-
-> FeS0 4
CuS0 4 + Cu
Calculate the molar concentration of the acid and its concentration in -* Fe 2+
Fe + Cu* + -f-Cu
g/dm*. (Na,CO, - 106; HC1 - 36.5.)
25.0 cm* of a solution of sodium hydroxide containing 10.0 g in
8. Zn + 2AgN0 3 -* Zn(N0 3 ) a + 2Ag
1 dm*required 24.0 cm' of dilute sulphuric acid for neutralisation. Cal- Zn + 2Ag+ -v Zn2+ + 2Ag
culate the molar concentration of the acid and its concentration in g/dm*.
(NaOH = 40,H,S04 = 98.) We can arrange the metals in a series such that any metal higher up
9. 1.00 g of pure ammonium chloride was boiled with 20.0 cm' of a in the series will displace from its salts any metal below it. The greater
solution of sodium hydroxide until the evolution of ammonia had ceased. the gap separating the metals in the series, the more readily does
If the resulting solution required 1 1.0 cm* of 0.1 M
hydrochloric acid for displacement take place.
neutralisation, calculate (a) the volume of ammonia gas evolved at
s.t.p., (b) the molar concentration of the sodium hydroxide solution.
Again, if a plate of zinc and a plate of copper are immersed in dilute
(NH 4 C1 = 53.5; one mole of any gaseous compound occupies 22.4 dm* sulphuric acid, a current will flow from the copper to the zinc outside
at s.t.p.) the cell and from the zinc to the copper inside the cell, if the plates
10.Describe how you would transfer exactly 25 cm* of a molar solution are connected by a wire. Thus the copper and the zinc must be at
of sodium carbonate to a conical flask, using a pipette. How would you different potentials when in contact with dilute sulphuric acid. These
then set up and fill a wet burette with a given sample of dilute sulphuric
potentials can be measured and by arranging the metals according to
acid and titrate the acid against the sodium carbonate solution? Mention
throughout the precautions you would observe to secure accuracy and state this potential difference the same series is obtained as by the displace-
the name and colour change of the indicator you would use. If 37.5 cm' ment method. The list obtained is as follows, omitting the less
of acid were needed for the titration, what is the molar concentration of common metals:
the acid?
how many cm' of 0.5
11. Calculate M
sulphuric acid will be used in the METAL SYMBOL
of 25.0 cm' of a solution which contains 70 g of sodium hydrogen
titration
carbonate in 1 dm' of solution. State the molar concentration of the sodium Potassium K Most electropositive metal.

hydrogen carbonate solution. (H — 1, Na — 23, C —

12, O — 16.) Calcium Ca
12. A sample of concentrated hydrochloric acid has a density
typical Sodium Na
-
of 1.16 g cm ' and contains 32.0% of hydrogen chloride. What volume of Magnesium Mg
this liquid would be needed to make 2 dm* of M
hydrochloric add? Aluminium Al
133
134 A NEW CERTIFICATE CHEMISTRY THE ELECTROCHEMICAL SBRIES 135

METAL SYMBOL The behaviour of metals in liberating hydrogen from water or

Zinc Zn dilute acid is a special case of this relation. All metals which are more
Iron Fe electropositive than hydrogen displace it; the most electropositive
Lead Pb metals, e.g., Na, K, Ca, displace hydrogen from water. As electro-
(Hydrogen) H positive nature decreases, metals require dilute acid, e.g., Zn, Fe,
Copper Cu while lead (very close to hydrogen in the electrochemical series)
Mercury Hg requires hot, concentrated hydrochloric acid. In all these cases, the
Silver Ag metallic atom ionises by supplying a number of electrons equal to its
Gold Au L
I east electropositive metal. valency to hydrogen ions present in water or acid. These ions are
converted to hydrogen atoms and, by pairing, to molecules which are
Hydrogen, although not a metal, is placed in the series to indicate the liberated. For example,
position it would occupy.
—
Na- - e~ » Na + ; + H +
e~ -> |H 2 (water)
It will probably strike you at once that the metals occurring above Zn- -2e- —* Zn 2+ 2H + + 2e~ -+ H (dilute HC1)
2

hydrogen liberate that element from acids with an ease indicated by
the interval separating the metal from hydrogen in the series. Thus
magnesium and zinc liberate hydrogen readily (so would sodium and
potassium, with such an 'ease' that the experiment would be danger-
ous), whereas copper, which is below hydrogen in the series, does not
liberate hydrogen from acids at all.
Chemical activity of the more electropositive elements
Metals such as sodium and potassium, which occupy positions high
up in the series, are said to be very electropositive. These metals are
very active chemically, and metals lower in the series are less active.
In modern terms, this means that the more electropositive metals
ionise readily by loss of electrons, e.g.,
Al- -3e~ Al 3 '; 3H+ + 3e- ->- liH, (dilute HC1)
Copper and silver are less electropositive than hydrogen. They cannot
displace it from water or acid. They are attacked by no mineral
acid except a strongly oxidising compound such as nitric acid or hot,
concentrated sulphuric acid.
In general the more electropositive metals oxidise readily, while
the least electropositive tend to be inactive; for example, copper and
silver are not readily attacked by the oxygen of the atmosphere. They
have been found as free metals in the earth's crust and used as coinage
metals.The more electropositive metals do not occur free in nature
but only as compounds, such as sodium chloride, zinc sulphide and
aluminium oxide.

- Gradation in properties of compounds of metals according to position

Na-e--)-Na + ; Ca 2e~ -* Ca,+
in the series
The less electropositive metals ionise much less readily. One result of
Not only does the series give usa good estimate of the chemical
this relation is that, if conditions are similar and neither metal is
activity of the metal itself, but in many cases the properties of com-
affected by water, a more electropositive metal will displace a less
electropositive metal from its salt in solution, e.g., pounds of the metals are graded according to the position of the metal
in the series. Thus the nitrates of sodium and potassium on heating
Zn + CuSO« —* ZnSO« + Cu decompose to the nitrite, the remainder of the metals of the series as
The essential feature of this relation is that the zinc atom (more far as copper (inclusive) form nitrates which decompose into the
electropositive) transfers two electrons to the copper ion in solution, oxides on heating, liberating nitrogen dioxide and oxygen. The lowest
which is converted to a copper atom and precipitated. The changes members of the series, mercury, silver and gold, form nitrates which
are: decompose to the metal on heating. (See p. 518.)
Zn -» Zn*+ + 2e~; Cu s+ + 2e~ -> Cu The following table shows some of these properties of the metals
or, added together, and their compounds. It will be noticed that, as a rule, a change
occurs in the region of calcium and another change in the region of
Zn + Cu 2+ -> Zn*+ + Cu copper. Be careful not to be too dogmatic about the properties as
-
The zinc ion is left in solution in association with the SO«* ion, as indicated in this way. Some metals show 'false' behaviour by ac-
the salt, zinc sulphate. For galvanic couple, see p. 151. quiring, in air, a coherent coating of oxide which renders them
 BLECTROLYSIS 137

u
If
a1 m
111
t/j —j
if flip
n
lill'L
iliSp
inactive, e.g., ordinary
dilute sulphuric acid. If,
aluminium foil is inert towards air, water or
however, it is dipped into mercuric chloride
solution, a layer of amalgam forms and an oxide layer cannot cohere
on the foil. Then the metal attacks both water and acid, and rapidly
si * throws off flakes of oxide in air at ordinary temperature.

Jif 2A1 + 6H + ->- 2A1S+ + 3H,; 4A1 + 30, - 2AI,0 3

Z§ ° z as
The place of non-metals in the series

A has been worked out to include

list common non-metals and is

hi If given below.

Electropositive
8 Potassium
Calcium
I!
pfil is.So egi Sodium
Magnesium
Aluminium In this complete series, the
S54 Zinc further apart two elements arc,
I S3 BS|i| METALS Iron the more likely they are to
egg 8fr
s Lead form a stable compound. Thus
(Hydrogen) oxygen combines very readily
Copper with sodium and potassium.
ill Mercury Elements close to one another
811 4i
Silver either do not combine at all or
Gold form unstable compounds.
Thus chlorine dioxide, C10„
ill
Carbon an unstable explosive sub-
371?.
if* 1*1 Nitrogen
is

stance. Metals do not form

Phosphorus stable compounds with each
««
O 60
-"8
NON- Sulphur
i £ J «
METALS other.
ra.o — 5 Oxygen
s -o so
< < s Chlorine
i Fluorine
a 1
Hi 9 g.° S Electronegative
4 o s — ffl_-

1 till
"Sg
ELECTROLYSIS
•E-S* 8?
Ills Electrolysis is the decomposition of a compound (molten or in
n alia solution) by the passage through it of an electric current.
S£
z^ Electrolytes and non-electrolytes
3
* <5 z" f 5 < 3 5 oe
Consider the apparatus of Fig. 38. By varying the liquid in the
beaker, three results can be obtained.
 138 A NEW CERTIFICATE CHEMISTRY THE IONIC THEORY 139

1. If the liquid in the beaker is alcohol, ether, chloroform, benzene Definitions

or turpentine (to select a few from thousands of similar liquids) the compound in solution or a molten compound
An electrolyte is a
ammeter will show no current passing, whatever increase may be conduct electric current with decomposition at the elec-
which will
made in the voltage used, and no chemical action will occur at the
trodes as it does so.
electrodes. These substances are called non-electrolytes.
A non-electrolyte is a solution or a molten compound which cannot
be decomposed by an electric current.
The electrodes are two poles of carbon or metal by which the
current enters or leaves an electrolyte.
The anode is the positive electrode by which the current enters.
The cathode is the negative electrode by which the current leaves.

THE IONIC THEORY

To account for the phenomena of electrolysis the Ionic Theory was
put forward by Arrhenius about 1880.
Ammeter Electrolytes. These substances are believed to
contain electrically

charged particles called ions.

Ions are derived from atoms (or groups of
atoms) but differ from
charges are positive for
them by possessing electrical charges. These
hydrogen ions and ions derived from metals (or metallic groups like
for ions derived from non-metals or acidic radicals.
NH*), and negative
the
The number of electrical charges carried by an ion is equal to
valency of the corresponding atom or group.
Electrodes
Some examples of ionisation are:
If the liquid is alcohol, If the liquid is a solution
eiher, chloroform or IONS
benzene,
of any acid, alkali or salt COMPOUND
in water,
Voltameter Sulphuric acid 2H + so«2 -
the current will the current will pass and Sodium chloride Na + ci-
NOT pass. decomposition will occur. Sodium hydroxide Na + OH-
Fig. 38.
Copper sulphate Cu2 + so 42 -
Experiment to show the difference between an electrolyte and a non-electrolyte
Lead nitrate Pb*+ 2N0 3 -

Hydrochloric acid H+ ci-

2. If the liquid in the beaker isan aqueous solution of any mineral
It isvery important to notice that an ion is very different
from the
acid, caustic alkali or salt, the ammeter will indicate the passage of a
corresponding atom, as was explained in Chapter 8. A metallic ion
large current and chemical decomposition will take place at the elec-
is formed from the atom by loss of a number of electrons equal to the
trodes. These substances are called strong electrolytes.
3. If the liquid in the beaker is pure water and a very high voltage
valency of the metal. Similarly, a non-metallic ion is formed from
the corresponding atom by gain of a number of electrons equal to the
is applied, a sensitive ammeter will register a current but it will be
very small and the corresponding chemical decomposition at the valency of the atom, e.g.,
electrodes will be very slight. There also exist a large number of com- NON-METAL
METAL
pounds which, if dissolved in the water, will increase its conductivity,
to a very small extent. Water, and substances of this type, are called K — e~ — K + (univalent) iCl, + e-->Ci-

weak electrolytes. Ca - 2e~ —» Ca2+ (divalent) S + 2e--*-Sg -

 140 A NEW CBRTIFICATB CHEMISTRY ELECTROLYSIS 141

for every molecule of

These electronic changes give to the ions properties quite different Exact measurement shows that in pure water,
from those of the corresponding (electrically neutral) atoms. water ionised, furnishing one hydrogen ion and one hydroxyl ion,
For example, by dissolving ordinary, electrically neutral, molecular there are 600 000 000 molecules of
water not ionised. The electrical
very
chlorine in water, a solution is produced which is yellow in colour conductivity of water, arising from these quantities of ions, is
and is a vigorous bleaching agent, but a solution containing clilorine small, but, even so, it must be clearly borne in mind that water is an

ions has neither of these properties. Similarly, ordinary metallic electrolyte and has a small, but measurable, electrical conductivity.
sodium, made up of neutral sodium atoms, attacks water liberating Further, by electrical or chemical action hydrogen or hydroxyl
if
ionise. So, while at any
hydrogen, but sodium ions, Na + , have no such action upon water. ions are removed, more water molecules can
- concentrations in water are very small, the
During the change, moment H + and OH
Na + ±Cl 8 -»-Na + Cl- water is potentially capable of yielding more of either ion as circum-
1
the loss of an electron by Na and the gain of an electron by CI causes stances may demand.
the ionic particles, Na + and CI" to assume a very stable, inert condi-
Mechanism of electrolysis. Electrolysis of cone hydrochloric acid
tion; hence their inactivity.
In strong electrolytes, the ionisation is complete. Thus, there exist The apparatus of Fig. 39 is suitable. The products are collected

over calcium chloride solution because both are insoluble

ina solution of common salt no molecules, NaCI, but only ions, Na + in it.
switched gas be found to collect in both
and Cl~. All strong electrolytes, i.e., salts, the mineral acids and the When the current is on, will

caustic alkalis, are in this state of complete ionisation tubes, which were full of saturated
calcium chloride solution at the
in dilute
solution. beginning. Equal volumes of gas will collect in the two tubes.
In weak electrolytes, ionisation is only slight and most of the When sufficient gas has accumulated, disconnect the U-tube after
electrolyte exists in solution in the form of unionised molecules; for switching off the current.
example, ordinary bench (2M) acetic acid, out of every 1000 mole-
in At the cathode, the gas will be colourless and can be tested by
hydrogen.
cules present, four are ionised and 996 are unionised. applying a light to it when it will burn in air. The gas is
gas be pale yellowish-green. This gas can be
CH 3COOH ^ CH COO- + H + 3
At the anode, the will
which be bleached. It is chlorine.
A solution of ammonia in water is also a weak electrolyte, contain- tested by damp litmus paper, will

ing a relatively small proportion of ammonium and hydroxyl ions.

Explanation of electrolysis by the Ionic Theory
NH«OH ^
NH< + OH- + So far we have seen that hydrochloric acid contains hydrogen ions
Most of the organic acids are weak electrolytes, e.g., tartaric, citric and chlorine ions. The concentration of hydroxyl ion from water is
and carbonic. It is not possible to draw an absolutely sharp dividing so small that it plays no significant part in this electrolysis.
linebetween strong and weak electrolytes, e.g., trichloracetic acid is When no current is passing, the ions are wandering aimlessly about
more highly ionised than acetic acid but much and, im-
is less highly ionised in the solution (Fig. 40). The electrical circuit is closed
than hydrochloric acid, and so lies between them in strength. For anode
mediately, the cathode becomes charged negatively, and the
your present purpose, the strong electrolytes are the only group attracts to itself the positive ions (that is, the
of positively. The cathode
considerable importance.
hydrogen ions) whilst the anode attracts the negative ions (that is, the
Non-electrolytes exist only in the form of molecules and are
in- chlorine ions). procession begins, hydrogen ions to the negative
A
capable of ionisation, for example,
pole, chlorine ions to the positive pole.
Chloroform CHCI 8 1
The exact position is as follows:
Cane sugar CijHo.Oh In pure water,
Alcohol C,H6 OH [H+] = [OH-1 = 10-' mole/dm* (at 25T)
Urea CONgH, .•. [H+HOH-] = 10-" = Ktt> (a constant).
Ktv is called the ionic product of water and is always maintained in aqueous
Water as an electrolyte
If H+ or OH - is withdrawn, water will ionise further to restore the value of
Water is an electrolyte but is very weak. Kk>. When [H+l = fOH"J = 10"', the liquid is in the same condition as pure
water, neutral; +
if [H l is greater than 10-', it is acidic; if [H+] is less than
H O ^ H+ + OH-
s 10-',
i.e.,
it is alkaline. But the product [H+l x [OH"] is always 10-".
142 A NEW CERTIFICATE CHEMISTRY ELECTROLYSIS 143

The positive hydrogen ions strike the negative pole and acquire
from it make them electrically neutral, and they
electrons which
become way ordinary atoms of hydrogen which link up into
in this
anode molecules and become ordinary gaseous hydrogen.
l fcarbon)
Note that is the electron from the cathode which
it

hydrogen ion and makes the latter become

neutralises the
an atom instead of an ion.

Similarly, the chlorine ion, negatively charged, comes into contact

with the anode, loses its electron and becomes an atom of ordinary
chlorine. Pairs of these atoms combine and become molecules of
ordinary gaseous chlorine, which comes off as a greenish gas. Thus
hydrogen^ chlnrioe the process can be summed up
Hydrogen chloride yields ions H + and CI - on solution in water; no
current is passing. When current passes and electrolysis begins,

saturated H+ + e--»-H CI- - e~ -+ CI

solution of ion atom ion atom
calcium uncharged uncharged
chloride
H + H-»-H a CI + CI -* c\ t
molecule molecule
At cathode At anode
Hydrogen 1 vol. Chlorine 1 vol.

It should be noted here (see also p. 162) that a cathode, as a source

of electrons,is equivalent to a reducing agent, and that discharge of

positively charged ions at a cathode is, chemically, a reduction. The

hydrogen ion, for example, is reduced (by electron gain) to the
Fio. 39.
hydrogen atom: H + + e~— »• H. The electron is supplied by the
cathode. Similarly, discharge of metallic ions at a cathode is, in all

cases, a reduction to the ordinary atomic state of the metal, as:

Na + + <r -> Na or Al3+ + 3«r ^ Al

9 e Ions of hydrogen and
chlorine wandering Correspondingly, an anode, as an electron acceptor, is equivalent
© i e
freely through
solution.
the
to an oxidising agent. Discharge of negatively charged ions at an

© © anode is an oxidation. For example, chloride ion, Cl~, is oxidised to

the atom by electron loss, the electron being accepted by the anode,

Catnode — + Anode
as:

Cl--e--*-Cl
•0 «© ©H The arrows indicate
the direction of move-
©.^ «! ment of the ions when
-0 ©©» charged plates are
placed in the solution. SELECTIVE DISCHARGE OF IONS
©.©-0
When two or more ions of similar charge are present under similar
conditions in a solution, e.g., H and Na or OH~ and S0 4
Fio. 40. + + *-, one is
,
 —

144 A NEW CERTIFICATE CHEMISTRY ELECTROLYSIS 145

preferentially selected for discharge and the selection of the ion dis- With platinum cathode, H* is discharged in accordance with the
charged depends on the following factors: series, Na
+ being higher in the series.
order of the electrochemical

1. Position of the metal or group in the electrochemical series

The cathode product is hydrogen gas (see p. 148).
used, there the possibility of discharging
If a mercury cathode is is

+ to form sodium amalgam with the mercury. This requires less

CATIONS ANIONS Na
K+
Caa+
Na +
Mg* +
Zn 2+ so 4 «-
Fe s+ no 3 -
To CATHODE «- Pb 8+ Cl- -+ To
H+ Br- ANODE far
OB* I-
Ag+ OH- "%%*-
Consider the arrangement given above which is the same as that of
the electrochemical series. If all other factors (see below) are constant,
any ion will be discharged from solution in preference to those above Dilute ,

4 sulphuric
it, positive ions at the cathode and negative ions
anode. For
at the
example, in caustic soda solution, containing positive ions H + (from
water) and Na + H
+ discharges in preference
, to Na + ; in copper
sulphate solution, containing OH-
(from water) and S0 4 *- as
-
negative ions, OH
is discharged in preference to S0 *~.
4
Platinum
The more important ions are printed in heavy type in the table.

2. Concentration
Increase of concentration of an ion tends to promote its discharge,
e.g., in concentrated hydrochloric acid, containing
_
OH"
(from water)
and Cl as negative ions, the concentration _
of Cl is overwhelmingly
the greater of the two. In these circumstances, CI - is discharged in Cathode,
-
preference. But, if the acid is very dilute, some discharge of may OH
also occur. F10. 41.
This
the only case you will meet at present in which the order of
is

discharge stated by the electrochemical series is reversed by a con- energy than the discharge of H+ to hydrogen gas and so occurs in
centration effect. The same
case arises in the electrolysis of sodium preference, and sodium amalgam is the product (see p. 253).
chloride solution, because the same anions are involved. The products of electrolysis of some important and typical solu-

tions will now be considered.

3. Nature of the electrode

Electrolysis of dilute sulphuric acid (so-called electrolysis
of water)
This factor may sometimes influence the choice of ion for dis-
charge. The most important contrast is electrolysis of a solution of The apparatus used is shown in Fig. 41. Both electrodes are
sodium chloride, with mercury cathode and with platinum cathode. platinum foil.
 146 A NBW CBRTIFICATB CHEMISTRY ELECTROLYSIS 147

The following ions are present: Electrolysis of caustic soda (sodium hydroxide) solution

The apparatus is the same as for the electrolysis of dilute sulphuric

From sulphuric acid H + and S0 4 - 2
acid (p. 145). The electrodes are again platinum foil.
From water H + and OH- The ions present are

CATHODE ANODE From sodium hydroxide Na+ OH-

From water H+ OH-
W S0 4
2~
and OH~
CATHODE ANODE
\ Na +
migrates to the cathode, gains an both migrate to the anode, H+ OH-
electron and becomes a hydrogen where OH~, being lower in the
atom E.C. series, is discharged in
/
preference to S0 4 2 ", in spite of both ions migrate to the cathode. ions migrate to the anode and
H+ + e--»-H the high concentration of the H + , being lower in the E.C. discharge by loss of an electron.
Hydrogen atoms combine in latter. series, is discharged in preference
pairs to give molecules. to Na\ in spite of the high con- OH~-e- OH
OH--e--»-OH centration of the latter.
H + H->H S By interaction between the OH
By interaction between the OH H + e~
+ H groups, water and oxygen are
Migration of S0 4*~ to the groups, water and oxygen are produced.
anode and discharge of H + are produced. The hydrogen atoms then com-
equivalent to decrease of con-
bine in pairs to give molecules. OH + OH H 2 +O
centration of sulphuric acid. OH + OH H +o 2 O+O
O+O o 8 H + H-»-H 2
Migration of Na + to the cathode
Summary Discharge of OH - disturbs the
Hydrogen, 2 vol.
Discharge of H +
disturbs the and discharge of OH - are
ionic equilibrium of water. More ionic equilibrium of water. More equivalent to fall of concen-
Acidity decreasing. water ionises to restore it
water ionises to restore it. tration of sodium hydroxide.
HaO ^ H + + OH- H.O ^ H + + OH- Summary
Excess H
+ so produced, with in-
Excess OH -
so produced, with
Oxygen, 1 vol.
coming S0 4 8 -, is equivalent to + Alkalinity decreasing
incoming Na , is equivalent to
increased concentration of sul-
increase of concentration of
phuric acid.
sodium hydroxide.

Summary
Oxygen, 1 vol. Summary
Acidity increasing Hydrogen, 2 vol.
Alkalinity increasing.

The total acidity at anode and cathode together remains constant. The total alkalinity at anode and cathode together is constant.
The final result, 2 vol.of hydrogen at the cathode and 1 vol. of The process is equivalent to the electrolysis of water.
oxygen at the anode, is equivalent to the electrolysis of water.
148 A NEW CERTIFICATE CHEMISTRY ELECTROLYSIS 149

Electrolysis of sodium chloride solution Electrolysis of copper sulphate solution

The apparatus is the same as for concentrated hydrochloric acid The ions present are:
(p. 142)or dilute sulphuric acid (p. 145). The cathode may be platinum Cu 2+ S0 4 *~
From copper sulphate
(or carbon), but the anode must be carbon to resist attack by chlorine.
The ions present are:
From water W OH-

From sodium chloride Na + ci- CATHODE ANODE

From water H + OH-
Cu a+ so 4 2 -
H+ OH-
CATHODE ANODE
\
Na + ci- Platinum anode
both migrate to the cathode.
H+ OH- Cu 8+ , being lower in the E.C. See the exactly similar case of
discharges in preference dilute sulphuric acid (p. 145).
/ series,
to H+ .

both migrate to cathode. , H + both migrate to the anode. Cl~ Cu* + + 2e" — »- Cu Summary
being lower in the E.C. series, is discharged because present in Oxygen given off.
The copper deposits as a brown Solution becomes with
discharges in preference to Na + . much greater concentration than acidic
layer.
H+ + <r-»-H
OH- (see p. 144). sulphuric acid.

Cl--e-->-Cl Summary Copper anode

Hydrogen molecules then are
Copper deposited.
formed by combination of the The atoms then combine in
With this anode, there are three
possibilities:
atoms in pairs. pairs to give molecules.
Discharge of S0 4 8 -] by
H + H - H,
1.

ci + a -» a, 2. Discharge of
-
OH loss of

+ 3. Conversion of Cu elec-
Discharge of H disturbs the
atom to Cu' + trons .

ionic equilibrium of water. More Summary

Oxygen The last of these occurs most
water ionises to restore it Chlorine, 1 vol.
*T Platinum readily. and OH" are
S0 4 *-
cathode I

H,0 ** H+ + OH- not discharged. Copper passes

into solution from the anode as
Excess OH -
so produced, with
Cu 2+ ions.
incoming Na + , is equivalent to
the presence of sodium hy-
Cu-2e-->-Cu ^, -

droxide.
Summary
Summary Copper passes into solution as
Hydrogen, 1 vol. ions. The total concentration of

Solution becomes alkaline by the solution in S0 42 ~ (not dis-

presence of sodium hydroxide. charged) and Cu 2+ (copper is
Copper copper sulphate
pfate depositing on the cathode) is
solution
constant. The electrolysis merely
Hydrogen and chlorine are produced in equal volumes. If the Fio. 42.
transfers copper from anode to
three-limbed voltameter is used, chlorine will have to saturate the Electrolysis of
copper sulphate solution. cathode.
brine first.
150 A NEW CERTIFICATE CHEMISTRY GALVANIC COUPLE 151

liberated by passing 96 500 coulombs this amount of electricity

SUMMARY OF THE EFFECTS OF ELECTROLYSIS hydrogen
is called
is ;

'faraday'. It follows from Faraday's Laws that one faraday

one
of electricity also liberates the equivalent weight in grams of any
other
Solution
electrolysed Cathode of Anode of At Cathode At Anode Another way of expressing Faraday's Law (3) as stated above avoids
the use of the term 'equivalent'. The reasoning
is as follows. In the case

of a univalent ion, such as Na+ or CI", one electron is involved

in its
Hydrochloric Carbon or Carbon Hydrogen Chlorine
acid (cone.) platinum one volume one volume discharge to form an atom.
—
Na+ + e~ * Na or CI" » iCU + «" —
Sulphuric acid Platinum Platinum Hydrogen Oxygen From follows that one mole of atoms of the element is obtained by
tnis, it

the passage of one faraday of electricity, i.e., the Avogadro

(dil.) 2 volumes; I volume; constant,
decrease of increase of 6.02 x 10*", of electrons. If the element is divalent (or trivalent),
one-half
acidity acidity
(or one-third) of a mole of atoms of it is obtained by
expending this
number of electrons, e.g.,
Caustic soda Platinum Platinum Hydrogen Oxygen iZn' + e~ -> }Zn1"
or iAl»+ +<?-—»• *A1
(sodium 2 volumes; 1 volume;
hydroxide) increase of decrease of Faraday's Law (3) then takes the following form:
alkalinity alkalinity
One faraday of electricity liberates, in electrolysis, either one
mole of atoms of an element or a simple submultiple of one mole.
Hydrogen
Common salt Platinum Carbon
1 volume;
Chlorine
One faraday of electricity is often referred to as a mole of electrons because
(sodium or carbon volume
sodium
1
it is able to liberate one mole of atoms (or one gram-atom) of a univalent
chloride)
hydroxide metal during electrolysis. (For electroplating, see p. 496.)
solution
Galvanic (or voltaic) couple
Copper Copper
sulphate (1)
Platinum Copper
deposited
Oxygen and A galvanic couple is an arrangement of two metals and an electrolyte
sulphuric acid
which can generate electric current. To operate effectively the two metals
must be widely separated in the electrochemical series, e.g., zinc and copper.
Copper Copper Copper Copper Copper If rods of these metals are placed in the electrolyte, dilute sulphuric acid,
sulphate (2) deposited dissolved and the metals are pure, nothing appreciable will occur so long as the metals
are not in contact. If, however, they are joined by an electrical conductor
such as a metallic wire (not in contact with the electrolyte), it will be found
Laws of electrolysis that current will flow in the wire from copper ( + ) to zinc (-), the zinc
will begin to dissolve in the electrolyte and hydrogen will appear as bubbles
The laws expressing the quantitative results of electrolysis were
on the copper. Zinc becomes a cathode and copper an anode in this voltaic
first stated by Faraday. They assert that the weight of an element cell.
liberated during electrolysis is proportional to To produce this result, zinc, the more electropositive of the two metals,
ionises by electron loss and the electrons pass from zinc to copper through
(1) the time of passing the steady current the wire. This is equivalent to the flow of conventional current in the
(2) the magnitude of the steady current passed opposite direction. At the copper surface, the electrons reduce hydrogen
ions from the electrolyte.
(3) the chemical equivalent of the element.
Zn—»-Zn ,+ + 2e~
The third statement is the most difficult to understand. It asserts, for 2H+ + 2e~ —* H,
example, that if, by passing a certain quantity of electricity through Theoretically, current can continue to flow as long as materials last; in
different electrolytes, hydrogen, copper, silver, chlorine and oxygen are practice, bubbles of hydrogen adhere to the copper, cut off much of its
given, then, if the weight of hydrogen liberated is l.OO&r g, the weight of contact with the electrolyte and so 'polarise' the cell.
copper will be 31.8* g, of silver 108x g, of chlorine 35.5* g, and of oxygen Acell of this kind is a device for converting chemical energy into
8a: g,these figures being proportional to the respective chemical equivalents electrical energy. As the above equations show, the whole process in the
of the elements. cell corresponds to the change:
If a current of one ampere flows for one second the quantity of electricity
Zn + 2H+—>-Zn ,+ + H,
conveyed is called one 'coulomb'. It has been found that the passage of
008 This occurs when zinc dissolves in dilute sulphuric acid and, normally,
one coulomb of electricity liberates r^=
1

96 500
g of hydrogen. So 1.008 g of chemical energy is made available from this change as heat in this cell. ;
152 A NEW CERTIFICATE CHEMISTRY
much of the chemical energy is converted to electrical energy as electrons
flow from zinc to copper through the connecting wire.

taclanchd cell

This a practicable form of 'primary' cell for producing electric

cell is
current, operates by using up the chemicals of which it is composed
i.e., it

and it cannot be recharged. Chapter 13

The cathode is a zinc rod or sheet; the anode is a carbon rod and the
electrolyte in which they are immersed is ammonium chloride solution.
When the cell is operating, zinc ionises by electron loss and zinc ions
dissolve in the electrolyte; the electrons pass round the external circuit,
performing useful work (e.g., lighting a small bulb or ringing a bell), and Types of Reactions
are absorbed at the anode. This causes discharge of ammonium ions from
the electrolyte, with formation of ammonia (in solution) and hydrogen.
At cathode At anode Combination
Zn —
Zn«+ + 2e~
>• 2NH«+ + 2e~ —* 2NH, + H, Decomposition
The anode is immersed in a porous pot containing manganese(lV) oxide
Displacement
to oxidise the hydrogen. Otherwise, bubbles of hydrogen adhering to the
anode would polarise the cell. Catalysis
Reversible Reactions
2Mn 4+ H, + + 20H-—»-2Mns+
+ 2H,0
Thermal Dissociation
In the so-called 'dry" Leclanche cell, the electrolyte is gelatinised to prevent
spilling and the cathode is usually sheet zinc, also acting as the cell case. Oxidation and Reduction
This cell will yield a small current continuously without serious polarisa- Double Decomposition
tion. Much larger currents can be obtained intermittently, intervals being
required to allow the cell to recover from polarisation. (For the lead
accumulator, see p. 189).
CHEMICAL reactions are recognised by certain phenomena
which accompany them. (See Chapter I.) They can again be
subdivided into classes of reactions, each of which has its own
QUESTIONS peculiarities.

1. What do you understand by the term 'electrolyte'? Describe experi-

ments to demonstrate the products formed in the electrolysis of solutions Combination
of (a) sulphuric acid; (b) sodium sulphate; (c) copper sulphate. (O. and C.) This takes place when two or more substances combine to form a
2. State Faraday's Laws of Electrolysis. Describe carefully what happens single substance.
when copper sulphate solution is electrolysed between (a) platinum and when heated form ferrous
Example 1. Iron and sulphur combine to
(b) copper electrodes, and when sodium chloride solution is electrolysed
between (a) platinum, and (b) carbon electrodes. (L.)
sulphide (iron(II) sulphide).

3. Give a general but concise account of the phenomena which occur Fe + S -* FeS
when a salt is dissolved in water and the solution is electrolysed. Example warm lead dioxide lowered into a gas-jar of
2. If is
Describe briefly two instances of the practical application of electrolysis.
(L.)
sulphur dioxide, the two compounds combine and lead sulphate is

formed.
4. When an aqueous solution of sodium nitrate is electrolysed with inert
electrodes, the products are hydrogen (2 vol.) at the cathode and oxygen PbO^ + SOa-^PbSO*
(1 vol.) at the anode. Also, the cathodic liquid becomes alkaline and the
anodic liquid acidic. Explain these results and write ionic equations in Decomposition
illustration.
This occurs when a compound splits up into simpler substances.
5. Explain why solid sodium chloride is a very poor electrical conductor
This change usually lakes place without the necessity for the presence
while, if melted, it conducts electric current readily. State the products of
electrolysis of molten sodium chloride and give ionic equations to account
of a second substance, and very often the action of heat is sufficient
for them. State and explain the different products obtained by electrolysis to cause the reaction to take place.
of a concentrated solution of sodium chloride in water. Example 1. If calcium carbonate (for example, marble) is heated
153
 154 A NEW CERTIFICATE CHEMISTRY TYPES OF RBACTIONS 155

in an open crucible to bright red heat, the calcium carbonate decom- ordinary temperature but the introduction of a local source of high
poses into calcium oxide (lime) and carbon dioxide. temperature, e.g., an electric spark, starts an explosive combination

CaC0 3 -* CaO of the two gases.

+ CO, Concentration. If the reagents involved in a chemical reaction have
Example!. If potassium chlorate is heated strongly decomposes homogeneous mixture, more
their concentrations increased in a
it
into potassium chloride and oxygen. collisions will occur and the reaction rate will
frequent molecular
2KC10 3 -»- 2KC1 + 30 a be thereby increased. A simple case of this occurs when addition of
some concentrated acid increases the rate of liberation of hydrogen
Displacement
by the action of zinc on dilute hydrochloric acid. In the case of mixed
This occurs when one element (or group) takes the place of pressure implies increase of concentration and
of gases, increase
another element (or group) in a compound. because of
tends to increase the rate of reaction between the gases
Example 1. If zinc is placed in copper(II) sulphate solution, copper Reactions the liquid or solid
more frequent molecular collisions. in
is displaced by the zinc and zinc sulphate is left in solution. influenced by pressure because liquids and solids
state are very little

Zn + CuSO t ->- ZnS0 4 + Cu are almost incompressible.

homogeneous, e.g., if a solid is reacting
Example 2. bubbled into potassium bromide solution,
If chlorine is If the reacting system is not
with a liquid, particle size may For example,
influence reaction rate.
the chlorine displaces bromine and a red bubble of bromine is formed.
moderately with bench sodium hydroxide
A solution of potassium chloride is left aluminium foil reacts
solution when warmed but powdered aluminium reacts rapidly from
2KBr + Cl t -»-2KCl-fBr 1
cold and will usually froth out of the test-tube spontaneously.
Reversible reactions 2A1 + 2NaOH + 6H 2 - 2NaAl(OH)< + 3H 2

This occurs because, for a given weight of metal, powder

offers a
Suppose that n molecules of a substance A can react with m mole-
much greater area to the reacting liquid than foil. In the limit, sub-
cules of a substanceB to produce x and y molecules respectively of
actual atoms or molecules (such as occurs in solution)
products C and D, the system being homogeneous (i.e., entirely division to
liquid or entirely gaseous). offers maximum opportunity for reaction.
Light is a source of energy and can influence the rate of some chem-
nA + mB ^xC + yD ical reactions considerably by energising some of
the molecules
As soon as a of C and D is formed, a reverse reaction will begin.
little involved. For example, the reaction between chlorine and hydrogen
At first the forward reaction will preponderate but, as C and D at ordinary pressure is negligible in darkness, slow in daylight but
accumulate, the reverse reaction will build up until an equilibrium explosive in sunlight (at room temperature). Also, light is vital to
position reached with forward and reverse reactions proceeding
is
the photosynthetic production of starch by plants from carbon di-
at the samerate. The composition of the mixture will then appear oxide and water (p. 186).
constant, though it is the net result of the two opposing reactions,
not a static situation. This kind of chemical behaviour (which Catalysis
is
very common) is called a reversible reaction. Several examples
of Catalysis is said to occur when the rate of a chemical reaction is
reversible reactions are considered a little later in this
chapter. altered by an agent (the catalyst) which is left unchanged in amount
Rate of reaction. The rate of a chemical reaction (that is, the and chemical nature at the end of the reaction.
in
amount of reaction occurring in unit time) is influenced by several Acatalyst usually increases the rate of a reaction and this is
factors such as temperature, pressure (if gas is involved), concentration called positive catalysis. It is found that, in a reversible reaction, a
of reagents, light and catalysis. given catalyst influences the rate of the forward and reverse reactions
Temperature. In general, rise of temperature tends to increase the equally. It has no influence on the actual equilibrium position which
rate of a chemical reaction by two factors: molecules of the reactants is reached; only enables the equilibrium to be attained more
it
move more rapidly at higher temperature, producing more frequent rapidly. position is determined by factors such as
The equilibrium
and more energetic collisions. For example, a mixture of hydrogen concentration of reactants, temperature and pressure, not by the
and oxygen (2:1 by volume) remains unchanged indefinitely at catalyst used.
156 A NEW CERTIFICATE CHEMISTRY CONTACT PROCESS 157

In general, a catalyst will function even though it is present in only Consider the important industrial conversion of sulphur dioxide
minute proportion, e.g., the rate of decomposition of hydrogen per- for the manufac-
to sulphur trioxide, a stage in the Contact Process
oxide is measurably increased by the introduction of one ten-millionth ture of sulphuric acid.
of its weight of finely divided platinum.
A catalyst may change its physical nature during a reaction, e.g.,
2S0 2 + 0,^ 2S0 3 (all reagents gaseous)

From left to right, this reaction is

exothermic, i.e., it liberates heat.
coarsely powdered manganese dioxide may become fine powder (in
the first example below) but it must be left chemically unchanged at Suppose that an equilibrium position has been reached at certain
the end of the reaction. temperature, pressure and concentrations of reactants.
Effect of temperature change. Suppose the temperature of the
Examples of positive catalysis reacting system to be lowered (with no other change). Le Chatelier's
Principle requires the system to react so as to oppose this change,
REACTION CATALYST
i.e., to raise the temperature again. To do this, heat must be liber-
1. Heating of potassium chlorate Manganese dioxide, Mn0 2 ated by causing more sulphur trioxide to be produced, i.e., lower
2KC10 3 -> 2KC1 + 30 2 (Manganese(IV) oxide) temperature is favourable to production of sulphur trioxide. At once
2. Synthesis of sulphur trioxide Vanadium pentoxide, V.0 6 the difficulty arises that lowering of temperature reduces the rate
2SO a + O, ^ 2SO, or platinum (powder) of reaction so increasing the time required for the production of
3. Synthesis of ammonia Reduced iron (powder) sulphur trioxide. For this reason a catalyst must be introduced,
N2 + 3H 2 ^ 2NH e.g., vanadium pentoxide, V 2 5 , which increases the rate of reaction
8
and makes it viable at a relatively low temperature (450°C) which is
4. Decomposition of hydrogen Manganese dioxide, Mn0 2
favourable to the production of sulphur trioxide. In general, low
peroxide or platinum powder
temperature gives an equilibrium favourable to an exothermic
2H 2 2 -»-2H 2 + 0, reaction but catalysis is needed to give a favourable reaction
rate.
A negative catalyst decreases the rate of a chemical reaction. This
It is obvious that, conversely, high temperature produces an
variety of catalysis occasionally used to suppress an unwanted
is
equilibrium favourable to an endothermic reaction. In this case, the
reaction (e.g., 2%
of alcohol in chloroform acts as negative catalyst
rate of reaction is also improved by the rise of temperature so a
for the oxidation of the chloroform to poisonous products by the
catalyst is not needed in principle. For example, in a now obsolete
air) but has obviously fewer uses than positive catalysis.
industrial process for making nitric acid, nitrogen and oxygen were
combined to form nitrogen monoxide (an endothermic reaction)
Chemical equilibrium
simply by passing them through an extended electric arc (temper-
It has already been mentioned (p. 154) that, in suitable conditions,
ature around 2200°C).
a reversible reaction will reach an equilibrium inwhich forward and
reverse reactions are proceeding at equal rates and the composition N»(g) + 0,(g) ^ 2NO(g) (L -»- R 180.6 kJ absorbed)

of the mixture is kept constant. The conditions affecting chemical Concentration of reactants. Suppose that, in the Contact Process
equilibrium will now be considered in relation to a few reversible reaction above, equilibrium has been reached in certain conditions
reactions of industrial or experimental importance. In the consider- and then the concentration of oxygen is raised (relative to sulphur
ation of such reactions, a very valuable contribution can be made by dioxide). Le Chatelier's Principle requires the system to react to
a rule known as Le Chatelier's Principle. It is very widely applied to oppose this change, i.e., to reduce the oxygen concentration towards
physical and chemical situations and, for the latter, takes the fol- its former level. This can only be done by combining it with sulphur

lowing form. dioxide to form sulphur trioxide, i.e., increased concentration of

oxygen favours conversion of more sulphur dioxide to trioxide.
If a chemical system equilibrium and one of the
is in
(Correspondingly, increased concentration of sulphur dioxide
factors involved in the equilibrium is altered, the equili-
favours conversion of more oxygen to sulphur trioxide.) In practice,
brium will shift so as to tend to annul the effect of the
the sulphur dioxide and air mixture used contains about three times
change.
as much oxygen as is theoretically required for the sulphur dioxide
158 A NEW CERTIFICATE CHEMISTRY TYPES OF REACTIONS 159

content. (Use of more air renders the product too dilute in sulphur equilibrium is determined mainly by the temperature employed.

trioxide.) Pressure iswithout influence on the equilibrium position because

Pressure. Pressure changes are significant only in reactions con- there is no change in the number of gaseous
molecules present as a
cerning gases because liquids and solids are almost incompressible. result of the reaction.
Taking the Contact Process reaction again, suppose that, in a system
in equilibrium in the gaseous state, pressure is increased (with no Reaction of water with bismuth chloride
other change). Le Chatelier's Principle requires the system to react This reaction gives visible evidence of reversibility. If dilute hydro-
to oppose the change, i.e., to reduce the pressure towards its former chloric acid is added carefully, with shaking, to a gram or two of

value. Since 2 molecules of sulphur dioxide and one molecule of bismuth carbonate, a colourless solution will ultimately be obtained
oxygen produce 2 molecules of sulphur trioxide, a total 3 volumes of containing bismuth chloride. If this solution is put into a large
sulphur dioxide and oxygen are converted to 2 volumes of sulphur beaker and water is carefully added with stirring, the liquid soon
trioxide (Avogadro's Law, T. and P. constant). That is, the system becomes turbid with the formation of a fine white precipitate of
must convert more sulphur dioxide and oxygen to sulphur trioxide bismuth oxychloride.
to reduce pressure by reducing volume. In general, if a given (entirely BiCl 3 + H O ^ BiOCl + 2HC1
t
gaseous) reaction proceeds with a reduction in the number of mole-
This occurs because addition of water increases its relative concen-
cules present, it is favoured by high pressure. (Conversely, gaseous
tration and forces the reversible reaction from left to right (as written
reactions involving increase in the number of molecules present are
above). In terms of Le Chatelier's Principle the system reacts so as
favoured by low pressure.) In practice, the Contact Process can reach
to tend to reduce the increased relative concentration of water. If
a satisfactory 98% yield of sulphur trioxide (calculated on the S0 2
concentrated hydrochloric acid is then added drop by drop with
used) without recourse to pressure above atmospheric but the similar
stirring,the turbidity can be cleared as the increased concentration
reaction for producing ammonia,
of hydrochloric acid forces the reaction from right to left (or, in terms
N 2 + 3H 2 v± 2NH 3 (4 vol -» 2 vol, T. and P. constant)
of Le Chatelier's Principle, as the system reacts to reduce the in-
uses 400 atm pressure or more. See also p. 431. creased concentration of hydrochloric acid). By alternate careful
additions of water and hydrochloric acid, the reaction can be shown
Reaction of iron with steam
to reverse itself several times (by alternate turbidity and clearance)
This reaction is usually performed by boiling water in a flask and until the dilution becomes too extreme for a precipitate to be seen.
passing steam over iron filings in an iron tube at bright red heat A thermal dissociation is a reversible reaction brought about by the
(p. 265). It produces hydrogen and tri-iron tetroxide and the reaction application of heat. Examples are the thermal dissociations of
is reversible. ammonium chloride and dinitrogen tetroxide.
3Fe(c) + 4H 2 0(g) «* Fe 3 4(c) + 4H 2 (g) NH Cl^NH +
4 a
HCl; N 2 4 ^2N0 2

In the conditions stated above, the reaction goes almost to com- In both cases, complete dissociation doubles the number of mole-
pletion from left to right in the sense that the iron can be converted cules and the volume (T. and P. constant). Consequently, since the
almost entirely to the oxide. This is so because incoming steam main- mass of material is unchanged and the volume is doubled, the vapour
tains its concentration at a high level (forcing the reaction from left density of the product is ultimately halved. For example, at about
to right) while hydrogen is swept out of the reaction tube and its 350°C, the vapour density of ammonium chloride is 14.5 against a
concentration continually tends towards zero (keeping the reverse required value of iNH 4Cl or 26.75 for NH
4 C1 molecules.
This
action slight). represents about 85% dissociation. Similarly, the vapour density of
If a current of hydrogen is passed over red-hot trifcrric tetroxide, dinitrogen tetroxide which is close to 46 just above its boiling-point
the conditions are reversed and the oxide can be almost completely (22°C), corresponding to molecules N 2 4 (92), gradually falls with
reduced to iron. temperature rise until, at about 150°C, it is about 23, corresponding
If the iron tube is sealed, an equilibrium will ultimately be set up to N0 2 (46) molecules.
At intermediate temperatures, mixtures of
with all four materials present and the forward and reverse reactions N a 4 and NOa molecules are
in equilibrium and give vapour densities
maintaining the equilibrium. The composition of the mixture at between 46 and 23. The gas also changes colour from pale yellow
160 A NEW CERTIFICATE CHEMISTRY TYPES OF REACTIONS 161

through reddish brown to almost black as temperature rises, and corresponding compound will precipitate. For example, if a solution
+
reverses the colours with cooling. containing sodium chloride (that is, the ions Na and CI") is mixed
_
The above data are for one atmosphere pressure. If an equili- with one containing silver nitrate (that is, the ions Ag+ and a ), NO
brium position exists at a certain temperature and pressure and then silver chloride precipitates. The change is represented in the
essential

the pressure is increased, Le Chatelier's principle requires both form: Ag + - *

CI — AgCl 4. . Ions Na + and NO„- remain in solu-
systems to oppose this change, i.e., reduce pressure towards its tion. Such reactions of ion aggregation are virtually irreversible
former value. This they can do by reducing the degree of dissociation. because the very low solubility of the precipitate suppresses any
This reduces the number of molecules present and so reduces volume possible reverse with the dissolved ions.
and pressure. Thus, in both cases, dissociation is reduced by in-
Oxidation and reduction
creased pressure at constant temperature; conversely, reduced
It is necessary to discuss the way in which the
pressure increases dissociation. use of these terms has
Thermal decomposition is the name given to the break-up of a developed before it is possible to give a concise definition of them.
compound by heat without any recombination on cooling. An Originally, reduction was a reaction in which some compound was
example is the conversion of ammonium nitrite to water and nitro- deprived of all, or part, of the oxygen it contained, and an oxidation
gen by heat. was a reaction in which a substance combined with oxygen. In the
NH N0 8 -»- 2H aO + N, reaction represented by the equation:
4

CuO-f- H 8 -»-Cu + H 8
Double decomposition
the hydrogen is oxidised to water and the copper oxide reduced to
This name has been given to reactions in which two compounds
copper. This is the simplest possible use of the terms.
take part, both are decomposed and two new substances formed by
The readiness with which hydrogen combines with oxygen to form
an exchange of radicals. Double decomposition reactions are always
water caused hydrogen to be regarded as a kind of 'chemical opposite'
of the type:
of oxygen; so the term oxidation was extended to include reactions in
A.B + C.D-»-A.D + C.B which a compound gave up some or all of its hydrogen as well as
For example: Cu.S0 4 + H 8 .S -> Cu.S + H 8 .S0 4 those in which it combined with oxygen. (This idea of oxidation is
Commonly, both die original compounds used in the reaction are analogous to the idea of enriching a man by relieving him of his
soluble in water, while, of the products formed, one (sulphuric acid) debts.) By this extension a reaction like the conversion of con-
is soluble and one (copper sulphide) is not. Usually the precipitated centrated hydrochloric acid to chlorine is called an oxidation because
compound is the one wanted, for it can easily be separated
which is two molecules of hydrogen chloride (2HC1) are converted to a mole-
and purified by filtration and washing. Less frequently, the im- cule of chlorine (Cl 8) by loss of hydrogen.
portant product of a double decomposition reaction is more volatile 2HCl + (0)->H + Cl»
8
than the other compounds concerned and is driven off either as a gas
The oxygen for this reaction is commonly supplied from manganese
or, by heating, as the vapour of a volatile liquid. For example:
dioxide (p. 355). A similar case is the oxidation of hydrogen sulphide
NaCl +H 8 SO« -*- NaHS0 4 + HC1 f to sulphur by, say, chlorine.
gas

KN0 3 + H S0 4 8
- KHSQ 4 HNO3
volatile
H 2 S + Cl 8 -*2HCl-r-S
A further extension of the idea of oxidation arose from the fact that
liquid certain elements exercisetwo or more different valencies. One of the
It must be observed, however, that, from the modern point of most important of these is iron, which exerts a valency of 2 in iron(II)
view, many reactions of 'double decomposition', especially those compounds and 3 in iron(III) compounds. Now the conversion of
occurring in solution, are regarded as taking place between com- iron(II) oxide, FeO, to iron(UI) oxide, Fe 8 3 is a clear and simple ,

pounds which are already fully ionised, so that no decomposition case of oxidation.
takes place. The situation is merely that, if the ions present in the
mixture can form an insoluble combination, they will do so, and the 2FeO + (O) -* Fe O 8 a
162 A NEW CERTIFICATE CHBMISTRY TYPES OF REACTIONS 163

But FeCl 8 and

and must occur simultaneously. The electrons lost by the reducing
all iron(ll) salts, for example, iron(II) chloride, ,

iron(II) sulphate, FeS0 4

correspond to, and can theoretically be
,
agent must be accepted by the oxidising agent present. The following
obtained by neutralisation from, iron(II) oxide; similarly, all iron(III) examples illustrate these ideas.
salts, for example, iron(III) chloride, FeCl 3 , or iron(III) sulphate, When magnesium oxidised by combination with oxygen, the
is
1.
Fe 2 (S0 4) 3 correspond to, and can theoretically be obtained by
,
metal is two electrons per atom. These electrons
oxidised by losing
neutralisation from, ferric oxide. So the term oxidation was ex- accepted by oxygen atoms, which are reduced as a result. Mag-
are
tended to include not only the conversion of iron(II) oxide to nesium (giving out electrons) is the reducing agent; oxygen (accept-
iron(III) oxide, but also the conversion of any iron(Il) compound to the oxidising agent.
ing electrons) is
an iron(III) compound. Thus, the conversion of iron(II) chloride to
iron(lll) chloride by chlorine
Mg-2e--»-Mgs+ ; *O t + 2e~ -»- O*-
2FeCl, + Cl a -»-2FeCla Magnesium oxide is a collection of Mg 2+ and Oa ~ ions in equal
numbers.
is spoken of as being an oxidation, although oxygen is not involved.
Notice that the combination of magnesium with chlorine or sulphur
Similar cases of oxidation are:
is a similar process, as:
2FeSO« + H„S0 + O 4 Fe t (S0 4) 3 +H 2
Mg + Cl 2 -* Mg* + .2C1-
iron(II) ironfni)
sulphate sulphate Mg + S -* Mg* + .S*-
2Fe(OH) 2 + H 0-r-0-1 2Fe(OH) 3 Chlorine and sulphur must, like oxygen, rank as oxidising agents;
iron(ll) iron(IH)
hydroxide hydroxide as before, magnesium is a reducing agent in these reactions. From
this point of view, any conversion of a metal to its ions is oxidation,
In such cases be noted that the oxidation always involves an
it will
i.e., electron loss; correspondingly, any
conversion of a non-metal to
increase in the proportion of those groups which are electronegative,
its ions reduction, i.e., electron gain.
is
that is, which migrate to the anode when the compound is electrolysed
2. If a metallic ion, e.g., the iron(Il) ion, Fe*+, is so treated that
(p. 144). Thus, there is a higher proportion of the electronegative
it loses a further electron, it is oxidised and is a reducing agent. The
Cl~ group in iron(III) chloride, FeCl 3 than in iron(II) chloride, FeCl s
, ,

and a higher proportion of the electronegative S(V - group in iron(III) process is:

sulphate, Fe 2 (S04) 3 , than in iron(H) sulphate, FeS0 4 To summarise .

Fe* + - e~ -> Fe 3+

the above development, we can say, so far, that oxidation has in- An iron(lll) ion is formed. An agent must be present, e.g., chlorine, to
cluded the following ideas accept the electrons made available by the ferrous ions. It acts as the

oxidising agent (electron acceptor) and is reduced.

1.

2.
3.
Combination with oxygen.
Removal of hydrogen.
Increase in the proportion of electronegative ion in a metallic
iCl, +e — Cl-

The complete reaction can be represented:

compound (which requires increase in the valency of the metal).
Reduction is the reverse effect in each case. Fe* + + iCl t
-»• Fe3+ + Cl~
Recently these ideas have been restated in electronic terms as It will be observed that the valency of the metal increases from 2 to 3
below, with considerable gain in simplicity in most cases. From the during the oxidation.
electronic point of view, the following definitions can be given: 3. The 'removal of hydrogen' aspect of oxidation is interpreted in

Oxidation is the process of electron loss. the following way. Consider the oxidation of hydrogen sulphide by

Reduction is the process of electron gain. chlorine. Hydrogen sulphide is slightly ionised as:
-
An oxidising agent is an acceptor of electrons. H aS ^ 2H+ + S2
A reducing agent is a donor of electrons. The sulphide ion parts with its two electrons and is, therefore,

Oxidation and reduction always occur together; they are com- oxidised, acting as a reducing agent.
plementary processes of electron loss and electron gain respectively Sa ~ - 2e- -*- S
164 A NEW CERTIFICATE CHEMISTRY TYPES OF REACTIONS 16S

The electrons are accepted by chlorine atoms, so that chlorine acts as loss) to the iron(IIl) state.
The iron(II) ions are oxidised (by electron
an oxidising agent and reducing agents
Below are mentioned some common oxidising and
is reduced.
exchange:
Cl 2 + 2e~ -»- 2C1- and their usual mode of operation in terms of electron

Adding the two equations, S 2_

+ Cl —* S + 2C1 -
2 . The hydrogen Oxidising agents
Reducing agents
ion of the hydrogen sulphide is unchanged.
Oxygen (p. 277) Hydrogen sulphide (p. 398)
The reduction of hot copper(Il) oxide by hydrogen
as:
4. is rendered
i 2 + 2e-->0*~ H 2 S ^ 2H + + S*-
S2 - -» S + 2e~
Cua+ .O s - +H 2
-*- Cu +HO a
404)
Chlorine (p. 362) Sulphur dioxide (aqueous) (p.

S0 2 + H 2 ^ H 2 SO a ^ 2H + S0 3
It is clear that the copper(II) ion is reduced by electron gain, as: + *-
iCl 2 + e--*-Cl-
Cu*+ + 2e~ -* Cu S0 3 *- + H O ->• S(V" + 2H + + 2e~
s
The two electrons are made available by the reaction between the
(with heated metallic oxides)
Ozonc 283) Hydrogen
oxide ion, O 2- and hydrogen: (p.
2-
+ 2e-->0 +
,

2
(p. 267)
O-+H a
2
-*• H2 + 2e~
3
0*--r-H 2 ->-H 2 + 2e-
By combining with oxygen in this way and supplying electrons to the
Hydrogen peroxide (p. 280) Carbon monoxide (with heated metal-
metallic ion, hydrogen exercises reducing properties. The oxide ion
is oxidised by electron loss and the oxygen atom remains in com- H 2 8 + 2H + + 2e—>2H 2 lie oxides) (p. 301)

bination with hydrogen as water. The H" is supplied by water 0*~ + CO — CO + 2e~
»- a

5. Nitric acid can operate as an oxidising agent, by accepting or dilute acid present in the
electrons, in several different ways. The two of greatest importance liquid.
are: Carbon (with heated metallic oxides)
Nitric acid (p. 438)
4HN0 3 + 2e~ ->- 2N0 3 " + 2H O + 2N0 2
t (i) (p. 290)
0»" + C -> CO
8HN0 3 + 6e~ -> 6N0 3 " + 4H O + 2NO
— CO+ +
2e~
a (ii)
4HNO, + 2e-->
The electrons are supplied by a reducing agent. A metal often acts in 2NO," + 2H 2 + 2N0 2 or 20»- + C s 4e"
this way, e.g.,
8HNO, + 6e~ -* t , . ,._.
Cu ->• Cu*+ + 2e~ 6NO - + 4H 2 + 2NO (For oxidation number, see p. 5Z/J
To supply the two electrons needed in equation (i), one copper atom electron-acceptors; all the
Notice that all the oxidising agents are
is required. This yields the reaction electron-donors. Examples of their oxidising or
reducing agents are
Cu -f 4HN0 3 -> Cu 2+ .(N0 3 -) + 2H 2 8 + 2N0 2 reducing action will be found on the pages quoted.
This is the chief reaction occurring when copper reacts with concen-
trated nitric acid. The products Exothermic and endothermic reactions
are copperfjl) nitrate, water and
accompanied by a
nitrogen dioxide. great majority of chemical reactions are
The
marked heat The above two types are distinguished.
To supply the six electrons needed in reaction (ii), three copper change.
atoms are required. This one during which heat is liberated to the
yields the reaction: An exothermic reaction is

3Cu + 8HNO a — >• 3(Cu 2+ .2N0 8 ~) + 4H 3 + 2NO surroundings.

This is the principal reaction when copper reacts with a mixture of e.g., the burning of hydrogen or carbon
concentrated nitric acid and water in equal volumes, and is the H + 40,(g) -* H tO(l);
t (g)
A/7 =
-286 kJ (-68.4 kcal) g-eqn" 1
recognised laboratory preparation of nitrogen monoxide, NO. This C(c) + ojffi -* CO^g); A// = -406 kJ (-97 kcal) g-eqn"*
gas is also the product when iron(II) sulphate solution is warmed Heat energy can be derived from coal, coke, coal-gas, petrol and
with nitric acid of suitable concentration paraffin, in the home or in industry, because the combustions of all
6Fea+ + 8HNO -» 6Fe * + 6NO " + 4H Q + 2NO
a
3
a
these substances are exothermic reactions.
2
166 A NEW CERTIFICATE CHEMISTRY TYPES OF REACTIONS 167

An cndothermic reaction is one during which heat is absorbed from water-equivalent of the whole system (bomb
the surroundings. •
calorimeter, water, thermometer, calori-
e.g., formation of nitrogen monoxide or carbon disulphide from meter, stirrer) is W
and the temperature
their elements. rise is t°C, the total evolution of heat is
Wt
the heated iron wire yields x cal in
*N 2 (g) + iOafe)-*" NO(g); AH = +90.3 kJ (+21.6 kcal) g-ean"' cal. If

C(c) + 2S(c) ->- CS AH = + 17 kJ (+28 kcal) g-eqn"

1
burning, the heat of combustion of a g of
2 (1) ;

material is (Wt — x) cal. The heat of com-

The symbol, AH, denotes the heat change taking place in the reaction compound is then
bustion of one mole of
corresponding to the equation to which it is attached (with gram units
of weight, i.e., g-equation -1 , and with stated physical condition of {Wt — x) x
M
— cal, where M is the molecular
reagents at constant pressure). The usual convention now used is to
weight of the compound. (This estimation is
refer the heat change to the reacting system, i.e., if heat is lost by
at constant volume since any change in the
the reacting system (an exothermic reaction), AH
is negative; if heat
capacity of the bomb calorimeter is negli-
is taken in by the reacting system (an endothermic reaction), AH is gible.) To convert to joules, multiply the
positive.
above quantity by 4.18. Fig. 43.
A kcal is a kilocalorie and is the heat required to raise the tempera- Bomb calorimeter.
ture of one kilogram of water by 1°C. This is one thousand times as
large as the ordinary calorie which raises the temperature of one Heat of neutralisation, solution and precipitation
gram of water by 1°C. J is the symbol for the joule, which is now Heat of neutralisation can be determined by the apparatus shown
replacing the calorie as the international unit of energy. The joule is
in Fig. 44. The apparatus is allowed to stand to attain a steady
expressed in electrical terms; thus, if one coulomb of electricity passes
temperature (which is read on the accurate thermometer). The test-
at an electrical pressure of one volt, the energy involved is one joule. tube is then broken, the acid alkali solutions mix and are stirred and
In general,
there is a temperature rise which is read on the thermometer. (Better,
volts x coulombs = joules the temperature can be read at 15 sec intervals and the results
The relation between the calorie and the joule is: rendered as a graph.) There are present 100 cm3 of solutions and
1 calorie = 4. 18 joule dilute solutions can be considered as having the same heat capacity

The symbol, kJ, represents 1000 joule.

as water. If the water-equivalent of the whole apparatus is g, and W
the temperature rise is t"C, the heat evolved by the reaction is
The following sections state in outline how some common therrao-
(100 + W)t cal. Since one-twentieth of a mole of acid and alkali is
chemical estimations can be made.
involved, the heat of neutralisation is (100 + W)t X 20 cal. (Multi-
ply by 4. 1 8 for joules.) As explained on p. 226, the heat of neutralisa-
Heat of combustion
tion of any strong acid by any strong alkali is a constant (13.7 kcal
For this determination, a bomb calorimeter is suitable. It is usually or 57.3 kJ).
made of steel (for strength), nickel-plated on the outside and pro- Heat of solution can be determined in the apparatus of Fig. 44, with
tected from oxidation by a coating of enamel or (better) gold leaf on a known weight, a g, of finely powdered solute in the inner tube and
the inside.A known weight (a g) of a compound is placed in the a known quantity of water (b cm 3 ) in the vacuum flask. The steady
platinum cup, C. Air is displaced by oxygen which is then allowed to temperature is read and the inner tube is broken. The solid is dis-
reach 20-25 atm pressure and the bomb is closed by a screw valve. solved with stirring and the final (usually lower) temperature is read.
The bomb is immersed in a known quantity of water in a well- The heat change is then (b +
W)t cal, where Wis the water equivalent
lagged calorimeter fitted with stirrer and accurate thermometer. Elec- of the apparatus and / is the observed temperature change. This is
tric current (through insulated platinum leads) heats the iron wire, T, the heat of dilution of the solute to a concentration of a g in b g or
which fires the experimental compound. This causes a sudden rise of cm 3 of water. It is also the heat of solution if the dilution is so great
temperature which is read on the thermometer (or, better, expressed that further dilution produces no further heat change, and if it is
on a temperature-time curve with readings at 15 sec intervals). If the referred to one mole of solute.
168 NEW CERTIFICATE CHEMISTRY QUESTIONS 169
A

Heat of precipitation can be determined in the same way as heat of between carbon and oxygen atoms in carbon dioxide and between
neutralisation, using any pair of solutions that can precipitate (com- hydrogen and oxygen atoms in water. These changes involve altera-
tions in electron orbits and, therefore, energy changes. Also, the
pletely for practical purposes) an 'insoluble' product, e.g., M
solu-
forces holding sugar molecules together in crystals are overcome and
tions of silver nitrate and sodium chloride. If 50 cm 3 of each are used,
the experiment and calculation is the same as for the neutralisation. replaced by forces holding water molecules together as liquid. At the
same time, molecules of carbon dioxide are left as gas and molecules
Ag'(aq) + Cl-(aq) -»- AgCI(c); A// = -65.7 kJ g-eqn">
of water as liquid, both types of molecule possessing energy of
motion. If these varying energy changes (and any others we may have
Thermometer
forgotten) arc allotted their correct signs and quantities, and account
is similarly taken of the heat energy liberated during the combustion,
Cottonwool
packing Stirrer the total energy change (obtained by adding these quantities to-
gether) must be zero.
The dissolution of a solid in water may be a purely physical change,
i.e., the separation of ions or molecules from crystals and
their dis-
persal into the water. This requires a supply of energy to overcome
Vacuum flask inter-ionic forces (as in a Na+Cl" lattice) or van der Waals forces (as
m many organic solids). This energy is taken from the water (as heat)
and the temperature falls, i.e., dissolution of a solid in water is often
endothermic. In some cases, however, chemical reaction occurs, e.g.,

ions may be hydrated, as with anhydrous copper(II) sulphate

Cu2+ +
4H.O -* (Cu.4H O) 2+ a
3 In such a case, this heat of hydration (added to the true heat of solu-
50cm of M NaOH
tion) may make the total change exothermic.

50cm3 of M HCI QUESTIONS

Give an account of catalysis, briefly referring to the catalytic oxida-
1.
tion of ammonia. Describe an experiment to show that the manganese
dioxide used in the ordinary laboratory preparation of oxygen from
potassium chlorate has not changed appreciably in weight during the
reaction.
2. What is a reducing agent ? Give three examples of common reducing
Fig. 44.
agents. Describe and explain any experiment in which sulphuric acid is
Heat of neutralisation. reduced. (O. and C.)
Conservation of energy. All energy changes which occur during 3. Describe and explain experiments in which the following substances
play the part of oxidising agents: (a) nitric acid; (b) copper oxide; (c)
chemical and physical changes of the kind considered above must
chlorine. How would you show practically that oxidation has occurred in
conform to the Law of Conservation of Energy; that is, energy can two of these cases you select? (O. and C.)
only be changed from one form into its equivalent of another form
4. Define reversible reaction, thermal decomposition and thermal dis-
with no total loss or gain. sociation. Describe any experiment you have seen to demonstrate thermal
To take the combustion of sucrose (cane sugar) to carbon dioxide dissociation.
and water as products (at ordinary temperature and pressure), we What happens when (a) lead nitrate; (6) mercuric oxide; (c) nitrogen
dioxide; (d) ammonium nitrate are heated? In each case state to which of
have the equation the above classes the reaction belongs, giving your reasons. (N.U.J.B.)
CmHmO^c) + 120 2 (g)-> 12CO s (g) + 11H.OG); —
State what type of reaction combination, double decomposition,
5.
AH = -5685 kJ or -1360 kcal g-eqn" 1 —
replacement, oxidation takes place when (a) sulphur is boiled with nitric
:

During this reaction, covalent bonds between carbon, hydrogen and acid; (fc) ammonia gas and hydrogen chloride are mixed; (c) chlorine is
1
passed into potassium iodide solution; (a ) hydrogen sulphide is passed into
oxygen atoms in the sugar molecules are replaced by covalent bonds
 .

170 A NEW CERTIFICATE CHEMISTRY

a solution of copper sulphate; (e) excess of carbon dioxide is passed
into
lime-water. (N.U.LB.)
6. Explain and illustrate by one example in each case the meaning
of
the terms: (a) reversible reaction; (6) catalyst; (c) allotropy;
(d) double
decomposition; (e) deliquescence; (/) synthesis. (L.)

'•, N (g)
1 + 3H 1(g)^2NH> (g) Chapter 14
lne large-scale manufacture of ammonia by the above reaction is catalysed
,

by iron. Select from the following possibilities the correct explanation of

its catalytic activity; the iron: (1) increases the rate
of the reaction left to
right only, (2) decreases the rate of the reaction right to left only,
(3) in-
creases the rate of both forward and reverse reactions,
(4) produces an
equilibrium mixture which is more concentrated with respect to ammonia.
Air, Combustion and Rusting
8. CH
3COOH(l) + C,H,OH(l) ^
CH,COOC,H,(l) +
H.Ofl)
This system (entirely liquid) will come to equilibrium at room temperature
and pressure in several hours, starting from one mole each of acetic acid STUDY of the air begins naturally with an examination of that
and ethanol. There is then two-thirds of a mole of ethyl acetate (and of
water) present. The reaction is catalysed by hydroxonium ion. State two
practical methods by which you would expect to obtain the equilibrium
A
common
most familiar of all chemical reactions— burning. Most of the
combustible materials (coal, wood, petrol) are complex com-
investigation.
mixture almost unchanged in composition but much more rapidly. State, pounds which are unsuitable as the starting-point of our
We shall fall back upon the metals, which are all elements, and,
and briefly explain, one method by which you would secure the conversion there-
of more than two-thirds of the acetic acid to ethyl acetate. State and materials known.
fore, the simplest
briefly explain the (qualitative) effect of adding more water to the equili-
brium mixture. What, if any, would be the effect on the equilibrium mixture
Effect of heating certain metals in air
of raising the pressure to 2 atmospheres?
9. The
reaction: 3Fe +
4H.O ^FejO, +
4H„ is reversible in con- Copper. Take up a piece of copper foil in a pair of tongs and hold
hot and, on cooling, is
ditions in which iron and its oxide are solid and the other reagents gaseous. it in a Bunsen flame. The metal becomes red
Describe and explain what occurs (a) if hydrogen is passed over red-hot black copper oxide. If the metal is
covered with a black layer. This is
tri-iron tetroxide in an open tube, (i) if steam is passed over red-hot iron powder and the fresh copper
in an open tube. If an equilibrium system exists among all these four
scraped, the surface layer is obtained as a
exposed can be similarly treated. In time, a quantity of the black
reagents in a closed vessel at red heat, what will be the (qualitative) effect, if
any, on the equilibrium of (c) adding more of the oxide of iron, (d) doubling powder can be obtained. .

crucible lid. It melts to shining

the total pressure, (e) doubling the partial pressure of hydrogen, tempera- Lead. Heat a little lead foil on a
ture being constant throughout ? Briefly explain your reasoning in each case.
beads of molten lead. Stir the beads. The metal gradually changes to
10. The reaction: N, + s O ^
2NO, is reversible and (from left to right) a yellow powder called litharge.
endothermic, all reagents being gaseous. Explain the term endothermic
Magnesium. Hold one end of a length of magnesium
ribbon in
reaction. If the above system is in equilibrium (at a temperature which
the other end in a Bunsen flame. The ribbon burns
allows quite rapid reaction), what, if any, will be the effect on the equili- tongs and place
brium of (a) doubling the total pressure, (6) doubling the partial pressure with a dazzling flame (it is rather dangerous to
look at it for any
of nitrogen, (c) lowering the temperature slightly? Explain briefly why this length of time) and leaves a white ash— magnesium oxide.
reaction (when used industrially) was not catalysed. What alternative was doubt the metals concerned have
These experiments leave no that
available?
change. The products left after heating them are
1 1 For each of the following, state one change of conditions (tempera- undergone a drastic
quite different from the original metals.
ture changes excluded) suitable for increasing the rate of reaction (a) com-
:

bination of hydrogen and chlorine, (/>) decomposition of hydrogen peroxide

solution, (c) displacement of hydrogen from hydrochloric acid by mag- The nature of the change
nesium. Hydrochloric acid is a stronger acid than sulphuric acid. What experiments to prove that air is
explanation in terms of chemical equilibrium can you give of the following It is hardly necessary to describe
concerned in this change. This can, however, quite readily be shown
facts: (a) addition of concentrated sulphuric acid to sodium chloride
liberates hydrogen chloride quantitatively, (b) addition of dilute sulphuric by taking the most combustible of these metals, magnesium, placing
acid precipitates barium sulphate quantitatively from barium chloride it in a crucible, filling the crucible with sand,
well pressed down to
solution?
exclude air, and heating the crucible to redness. On cooling, the

magnesium is unchanged.
 172 A NEW CERTIFICATE CHEMISTRY AIR, COMBUSTION AND RUSTING 173

Since air is concerned in the change, two possibilities have to be j s in a closed vessel, and, if possible, any change in the amount of
considered. The metals may have combined with something from air should be automatically shown to us by the apparatus. A
very
the air or they may have lost something, which has been taken up by simple arrangement satisfies this requirement. We shall confine the
the air. (A third possibility is that the change in the metals may be sample of air in a bell-jar over water (see Fig. 46). The water forms
due to some rearrangement of their material without loss or gain, but a flexible base to the bell-jar and will move up or
down inside the jar
this is unlikely since such a change could presumably occur without to show us what is happening to the amount of air inside. As a matter
air.) Clearly, in the first case, the material which had combined would of mere convenience we shall choose yellow phosphorus for our
make the weight of the product greater than that of the metal, while, burning substance this time. (Yellow phosphorus takes fire very
in the second case, the material lost would have the reverse effect. We readily and must be treated with great care. Never touch it with your
have only to weigh the metal before burning and the product after fingers. The heat of them may start it burning and the burns it will
burning to decide this point. cause are very severe and difficult to heal. Yellow phosphorus is
always kept under water because of the ease with which it takes lire.)
To find whether there is any change in weight when magnesium burns in
air
To find whether there is a diminution in the volume of the air when
Crucible Weigh a crucible (with lid) con- phosphorus burns in it

Magnesium taining about 0.5 g of magnesium.

Float a small porcelain dish on water in a pneumatic trough and
Set up the apparatus as in Fig. 45. put in it a piece of yellow phosphorus about as big as a pea. Place
Remove the lid and heat the crucible.
over it a bell-jar and adjust the water to level A
(Fig. 46, I), the
Pipe-clay When magnesium begins to burn,
the
stopper of the bell-jar being removed. The bell-jar above is A

A
put the lid on the crucible. Raise it
occasionally to allow air to enter to

Fig. 45.
burn the magnesium but, as far as
possible, avoid losing any 'smoke'
(fine particles of magnesium oxide)
which would tend to make the final
As
Burning magnesium in a weight too low. When all the
crucible. magnesium has burned allow the
crucible and lid to cool. Then weigh fhosphorai „ »

them again. There will be a gain in weight.

The products of combustion of a substance always weigh more than

the original substance.
This even true for coal. If we could collect all the ash, soot
is

smoke and the gases (carbon dioxide and steam) which escape up the Phosphorus just begin- After the phosphorus
ning to burn has burnt
chimney, they would weigh more than the original coal. (See p. 25.)
This gain in weight, which occurs no matter what the substance is Fio. 46.
that burns, at once establishes the point that, during burning, the The burning of phosphorus in air.

burning material combines with something. We now have to show

whether the 'something' comes from the air.
To do be necessary to find whether, when a substance
this, it will
burns in air, the air decreases in amount. We must devise an experi-
ment to test this point. It would be absurd to carry out the experiment
in the open laboratory into which air could leak from outside to
replace loss; we must secure a sample of air in a confined space, that
graduated into five equal portions. Heat a long iron needle in a
Bunscn flame, touch the phosphorus with it, withdraw the needle
quickly and insert the stopper of the bell-jar. The phosphorus burns
with a bright yellow flame, giving off dense white fumes of phos-
phorus pentoxide, which fill the jar. After a time the phosphorus no
longer burns. The water level inside the bell-jar will then be found to
 174 A NEW CERTIFICATE CHEMISTRY AIR, COMBUSTION AND RUSTING 175

rise1 and, when the bell-jar cold, the water level will stand at mark
is
2Cu + 0,-)-2CuO
copper(Ii) oxide
B on the jar (Fig. 46, II). Clearly, the rise of water inside the bell-jar
means that, during the burning of the phosphorus, some of the air
2Pb + O ->2PbO
a
lead(II) oxide
was used up to combine with the phosphorus.
After a time, the white fumes dissolve in the water, leaving the bell-
2Mg+ 2 ->-2MgO
magnesium
jar clear. It will then be seen that some unburnt phosphorus remains oxide
in the porcelain dish. This is very significant. The Same
extinguished for lack of phosphorus. We can see that some
was not P« +5O -*P O8 4 10
gas still phosphorus
remains in the bell-jar from the mark B upwards. This gas must be pentoxide
different from ordinary air because it will not allow phosphorus to
burn in it; it must also be different from the part of the air which has The smouldering of phosphorus
combined with the phosphorus because it will not do this. If a The chemical of the smoulder-
Phosphorus smoulders in air. effects
lighted splint Is plunged into the residual gas the splint is extinguished.
ing are very similar to those of the active burning of phosphorus
We are forced to conclude, therefore, that the air is not a single sub-
—
stance. It must contain at least two gases one which supports the
combustion of phosphorus and one which does not. Further, we may
conclude that the gas which is active in supporting the combustion of
the phosphorus constitutes about one-fifth of the air by volume (this
represents the rise of the water from A
to B) and the other gas about
These two gases have names. The one which supports
four-fifths.
f \ Yellow
-J—\—^phosphorv,
A Yellow
phosphorus
\no longer
smouldering

the combustion of phosphorus is called oxygen, the other nitrogen.

Let us sum up in a few sentences what we have learnt so far.

The principal gases in air are oxygen and nitrogen.

Oxygen constitutes about one-fifth of the air by volume and
nitrogen about four-fifths. During the combustion of a sub-
stance, it combines chemically with the oxygen of the air Phosphorus starting After several days
and the chemical combination is accompanied by the to smoulder
evolution of light and heat. The combination with oxygen Fio. 47.
causes a gain in weight. Nitrogen will not support com- Smouldering of phosphorus in an enclosed space.
bustion.

except for the time factor. This can be shown by an experiment for
By an experiment similar to the above,
can be shown that the
it which Fig. 47 is sufficient explanation.
material of a burning candle combines with oxygen and causes the
water-level inside the bell-jar to rise. The candle will not, More accurate determination of the proportion of oxygen in air by
however,
remove all the oxygen. volume
We may now give the equations for the chemical reactions con- we make use of the smouldering of phosphorus
In this experiment,
sidered in this chapter. to absorb the oxygen from a measured volume of air. (See also above.)
Take a graduated glass tube, closed at one end, fill it to a depth
W hj lethe of about 5 cm with water, close the open end with the thumb and
!.
Phosphorus is burning, the level of water inside the bell-jar will
r
fall.This is an expansion effect of the heated air. It is also necessary invert the tube in a deep jar of water. (If possible, allow the tube
to pour
water into the trough until the levels of water inside and outside to stand like this for several hours so that the air is saturated with
the bell-jar are
equal. If this is omitted we are not measuring the volumes
conditions.
^^
under the same water-vapour.) Adjust the level of water in the graduated tube to be
176 A NEW CERTIFICATE CHEMISTRY AIR, COMBUSTION AND RUSTING 177

YeJlovr the same as the level in the jar. Other gases present in air
Phosphorus The air inside the tube is then at
Carbon dioxide. Carbon dioxide is present in air to the extent of
atmospheric pressure. Read off
0.03% by volume. It is formed during the combustion of all the
the volume of air. Now push up
common fuels—coal, coke, coal-gas, water-gas, petrol, paraffin oil-
Air Nitrogen inside the tube a flexible wire carry-
all of which contain carbon.
ing a piece of yellow phosphorus
Wire, (Fig. 48, i). Read the temperature
c + o»-*co 2

of the laboratory and the barometer It is also breathed out as a waste product by all animals.
and set the apparatus aside until the In spite of the enormous quantities poured into the atmosphere in
phosphorus no longer smoulders. this way, the proportion of it remains constant, partly because carbon
The water level inside the tube will dioxide is taken up by the leaves of plants and converted to complex
have risen to C, the remaining gas starchy compounds (for a more complete discussion of this subject
being nitrogen (Fig. 48, ii). Remove and partly because it dissolves in the water of the oceans.
see p. 185)
the phosphorus and then lower The presence of carbon dioxide in the
71) flfl the graduated tube until C is at air can be shown by aspirating air Air Attached
Phosphorus After the phos- the level of water in the jar, giving through a boiling-tube containing a to Suction
beginning to phorus has ceased atmospheric pressure again inside pump
little lime-water. After a time the lime-
smoulder to smoulder
the tube. Read off the volume of water will go turbid, showing the pre-
Fio. 48. nitrogen. Take the temperature sence of carbon dioxide (Fig. 49).
To find the percentage by of the laboratory and read the
volume of oxygen in the air. barometer. Ca(OH) 2 4- CO -> CaCO s + H 2
a

The calculation of the percent- Water-vapour. This substance is

age of oxygen in the air by volume is given below. Lime
always present in the air in varying
Original volume of air = 70.5 cm 5 quantities. It is given off by evapora- \s water
Temperature 14°C Pressure 755 mm tion from the oceans, rivers and lakes.

Final volume of nitrogen = 55.0 cm 3 Its presence may be demonstrated by

Fio. 49.
Temperature 12°C Pressure 760 mm exposing some deliquescent substance,
Method of showing the
The volume of nitrogen must first be converted to the volume it say calcium chloride, to the air on a presence of carbon dioxide

would occupy at the same temperature and pressure as that of the clock-glass. A solution of the com- in the atmosphere.

original air.
pound be obtained after a day or
will
two. If this is distilled (see p. 191), the colourless liquid obtained
Volume of nitrogen at I4°C and 755 mm pressure
may be proved to be water by the tests given on pp. 270-1.
The rare gases. About 1 %
of the air by volume is made up of the
rare gases. The most abundant of them is argon, the others
being

= 55.8 cm 3 neon, xenon, krypton and helium. The proportion of each of the last
volume of oxygen = (70.5 - four is very minute. Argon and neon have found a use in 'gas-filled'
/. 55.8) cm3
= electric light bulbs and coloured 'neon' electrical signs. They are
14.7 cm3
obtained from liquid air.
.'. percentage of oxygen in the air by volume
Impurities. always contains small traces of many gases-
The air
_ 14.7 hydrogen sulphide, sulphur dioxide and others—especially in in-
X 100
70.5 dustrial areas. They are given off during the combustion of coal and
= 20.8 fuels derived from it. The tarnishing of silver is chiefly due to the
formation of a layer of black silver sulphide on it by the action of
In dry air, the correct percentage of oxygen is 20.9 by volume.
traces of atmospheric hydrogen sulphide.
178 A NEW CERTIFICATE CHEMISTRY AIR, COMBUSTION AND RUSTING 179

The following diagram summarises the composition of the air. The efflorescence of washing soda was noticed above. Another
efflorescent compound is Glauber's salt, sodium sulphate decahydrate,
AIR Na,SO 4 .10H a O. On exposure to air it loses the whole of its water of
crystallisation.
Iron(II) sulphate heptahydrate, FeS0 4 .7H aO, is also efflorescent, i.e.,
loses water of crystallisation on
exposure to air. In addition, it under-
goes oxidation by oxygen of the air, acquiring brown patches of basic
iron(M) sulphate.

NITROGEN OXYGEN CARBON WATER- RARE IMPURITIES

12FeS0 4 + 6H aO + 30, ->• 4{ Fe 8(S0 4) 3 .Fe(OH) 3 }
78.1% 20.9% DIOXIDH VAPOUR GASES H,S,SO„
by volume by volume 0.03% variable about 1% etc..
by volume by volume variable Composition of air by weight
This estimation was carried out by Dumas, 1841. Air was drawn
Exposure of some compounds to ordinary air through the following apparatus in the order shown (Fig. 50).
Sodium hydroxide. If exposed to air, sodium hydroxide absorbs
water-vapour from the air and forms a solution; that is, deliquescence Heated copper
occurs (p. 524). No chemical action is involved so far. The solution
then absorbs carbon dioxide from the air and forms a crystalline
solid, washing soda or sodium carbonate decahydrate.

2NaOH + CO, + 9H O ->- Na CO 3 .I0H O

s s 2

If left to stand, this solid will eventually lose nine ten molecules of its
of water of crystallisation (per molecule) to the air. That is, the
decahydrate effloresces, falling to a fine white powder consisting of
small crystals of the monohydrate, Na 8 C0 3 .H,0. Some sodium
bicarbonate may also be formed as the monohydrate absorbs carbon
dioxide from the air.
Fig. 50.
Na a C0 3 .H a O + CO -> 2NaHC0 3
a
Gravimetric composition of the air.
Calcium chloride deliquesces in air and forms a solution. This
tendency to absorb water-vapour explains the use of calcium chloride
as a drying agent for gases (not ammonia, with which it combines). 1. U-tubes containing potassium hydroxide to remove carbon
In this context, however, the relative amount of moisture is small dioxide (only one shown in the figure).
and the anhydrous calcium chloride is only hydrated to the solid 2. U-tubes containing concentrated sulphuric acid (on pumice)
hydrate, CaCI 3 .6H a O. This hydrate is also deliquescent. remove water-vapour (only one shown in the figure).
Phosphorus pentoxide deliquesces in air, forming a colourless solu- 3. A heated, weighed tube containing finely divided copper to
tion containing metaphosphoric acid. absorb oxygen;
P 4 O 10 + 2H O-*-4HPO
t 3 and, finally, the remaining 'atmospheric nitrogen* (still containing
The pentoxide is also used as a drying agent for gases, but not for the rare gases) entered aweighed evacuated globe.
alkaline gases like ammonia. The increase in weight of the copper gave the weight of oxygen,
Concentrated sulphuric acid absorbs water from the air, diluting and the increase in weight of the globe, the weight of nitrogen (and
itself, usually up to about three times the original volume. The acid rare gases).
is said to be hygroscopic (not deliquescent, this term being reserved Neglecting carbon dioxide, the percentage of oxygen by weight in
for solids which absorb water from the air to form solutions). dry, pure airis 23.2% the remainder being nitrogen and rare gases.
180 A NEW CERTIFICATE CHEMISTRY AIR, COMBUSTION AND RUSTING 181

Air— mixture or compound? c + ot -

CO,
The evidence on which a decision on this question can be reached
2H. + 0,- 2H.O
is given below: Then CuS0 4 + 5H,0 »- CuS0 .5H
4 2
white hydrated crystals;
blue
(1) The composition of air is very nearly, but not quite, constant.
Small, but definite, differences of composition have been de- Ca(OH) t + C(V CaC0 3 + H,0
chalk
tected when samples of air from different parts of the earth
have been analysed. to Filter -pump
(2) (a) If air is dissolved in water and boiled out again (see p. 193), or Aspirator
the percentage by volume of oxygen in the air boiled out is
increased from 21% to about 30%. No chemical reaction is
involved here; the composition of air has been altered by a
physical method, which depends merely on the fact that oxy- Lime water
gen is twice as soluble in water as is nitrogen.
(b) If liquid air is allowed to evaporate, nitrogen evaporates
more Here again, the
quickly, leaving almost pure oxygen.
gases of air are separated by a purely physical process.

This evidence alone is sufficient to decide that air is a mixture. rstneiti

White anhydrous
Canalt
Copper Sdlphate
Confirming it are the following facts:
Fio. 51.
(3) If nitrogen, oxygen, carbon dioxide, water-vapour and the To show the products of combustion of a candle.
rare gases are mixed in appropriate proportions, there is no
explosion, evolution of heat, volume change or other evidence the common fuels— coal, coke, coal-gas, petrol, paraffin
Most of
of chemical combination, but the product resembles ordinary water-gas—contain one or both of the same elements as candle-
oil,
air in every way. wax and their products of combustion consist mainly of carbon
(4) The composition of air corresponds to no simple chemical dioxideand water.
formula such as it would be expected to possess if it were a Though they pass off as gases, the products of combustion of a
compound. candle should weigh more than the candle-wax, which has burnt.

To show that the products of combustion of a candle weigh more than

The combustion of a candle
the candle-wax burnt
The products of combustion of a candle can be shown by the
The apparatus is described by Fig. 52.
apparatus of Fig. 51.
Suspend the apparatus from the balance hook of a large, rough
The products from the burning candle are drawn up the funnel and Light the candle. The
balance, and add weights to counterpoise it.
through the apparatus.
apparatus will quickly gain in weight and will depress the pan of the
Drops of liquid will condense in the U-tube and the anhydrous
balance to which it is attached.
copper sulphate will change to blue hydrated crystals. This proves
The gain in weight is the weight of oxygen from the air with which
that one of the products when a candle is burned is water. The lime-
the carbon and hydrogen of the candlewax have combined during
water will rapidly turn milky (the mil kiness is caused by a fine preci-
burning.
pitate of chalk). This proves that carbon dioxide is also given off
from the candle. Other kinds of combustion
Candle-wax contains carbon and hydrogen. During the burning, common that becomes
Combustions in oxygen or air are so it
these elements combine with oxygen of the air, forming carbon
almost habitual to use the word 'combustion' as if it referred to this
dioxide and water.
182 A NEW CERTIFICATE CHEMISTRY RUSTING 183

kind of reaction alone. Actually, it may be applied to any chemical find whether iron combines with anything from the air while
To
combination accompanied by light and heat in which one or more rusting
of the reactants are gaseous. You will find, for example, in this book,
This experiment is described by Fig. 53.
accounts of the combustion of hydrogen, phosphorus and copper in
chlorine gas.
To show the character of the gas left in the bell-jar in Fig. 53 (II),
fill up the
trough till level B rises to level A. Then remove the
stopper of the bell-jar and insert a lighted taper. It will be extin-

guished; the remaining gas is nitrogen. During rusting the iron has

^
combined with the oxygen of the air. This accounts for the rise in
Cottori wool
the water level (Fig. 53) and the gain in weight (see p. 182).
Ca/aum Chloride
—to absorb
water vapour

h—Cotton wool
Soda -lime Iron nails
to absorb
Carbon Dioxide
in a wet
muslin bag
Wire gauze

Candle- r/se oF
inside
<nsic'~
leve
'el
B
vJH&fcrT-i- li
Fig. 52. as
To show the increase in weight when a candle burns. II
Iron about to rust After rusting for three or four days
Oxygen of the air burning in coal-gas. An interesting reversal of Fig. 53.
the usual state of affairs, in which air is acting as the combustible The rusting of iron.

material, may be secured by using apparatus as in Fig. 97. (See

p. 303.) Rusting and burning are similar
It is important to understand clearly that, from the chemical
THE RUSTING OF IRON standpoint, rusting and burning are the same process. During burn-
ing, magnesium combines with oxygen of the air, forming magnesium
The important facts connected with the rusting of iron may be oxide.
ascertained by the following experiments.
2Mg-f-O t -»-2MgO
To any change During rusting, iron combines with oxygen of the air in the presence
find if there is in weight when iron rusts
Weigh a clock-glass containing some iron borings. Damp the bor- of water to form brown hydrated ferric oxide, 'rust'.

ingsand set them aside to rust. When rusted, place them in an oven 4Fe + 30 2 -*2Fe 2 3

to dry thoroughly, then weigh the clock-glass again. There will be The only difference time required for the two processes. Heat
is in the
a gain in weight. In this respect rusting is analogous to burning. We is generated during rusting just as it is during burning, but it is dis-
may now try an experiment to see whether the air is similarly sipated to the surroundings without attracting notice because of its
concerned in both. much slower rate of production.
 184 A NEW CERTIFICATE CHEMISTRY PHOTOSYNTHESIS 185

mankind of the stopper.) The water

It is very unfortunate for that iron, which possesses so will rise into the rubber tube. Place a clip
many useful properties, should
be so readily attacked by the oxygen in position to exclude all air.

of the air. To protect iron from rusting, it is painted or galvanised

Leave the test-tubes for several days. In neither case will
(see p. 483). The various protective processes probably cost at least
rusting occur. This means that iron will not rust in the
fifty million pounds annually over the whole world.
presence of air alone or of water alone; both are needed
We will now investigate further the conditions under which iron rusts. together to rust the iron.
We have already seen that during rusting, iron combines with oxygen
To make you have used are actually capable of
sure that the nails
of the air, and it is common knowledge that iron rusts more readily
rusting, put them a test-tube with a little water, leave the test-
into
when plenty of water is present. It will be of interest to separate
these agents and find their individual effects. To do this, we must tube open to the air and notice the result after a day or two.

expose iron to the action of air in the complete absence of water (to
What we have done in the above experiment is to take two sub-
stances, air and water, which normally act on iron together and test
water-free air) and to water in the complete absence of air (to air-
the effect of each singly. This is the favourite device of scientists. It
free water).
is only by finding out the effects produced by one agent at a time

that reliable information can be obtained.

To find the effect of exposing iron to air and water separately
(1) Exposure of iron to air separately. To do this, set up apparatus Oxygen and carbon dioxide in life-processes. Photosynthesis
as in Fig. 54, 1. The figure sufficiently explains the experiment. It can readily be shown that carbon dioxide is present in the air expelled
from the lungs of a human being. Use the apparatus of Fig. 55.
With the clip A open and the clip B closed, breathe in air through the
.Rubber tubing
mouthpiece M. The air bubbles through the lime-water in C. Then close
Up^Clip clip A, open clip B and breathe out the air so that it passes through the
lime-water in D. Repeat this several times. The. lime-water in C remains
unaffected while that in D is rapidly turned milky. This must mean that
Rubber
stopper *| .Rubber
stopper
during its occupation of the lungs, the air has increased its proportion of
carbon dioxide, which reacts with the lime-water in D
to form a precipitate
of chalk.
Ca(OH), + C0 3 -*-CaCOs + H.O
Air -tree At the same time, oxygen is absorbed from the air into the blood forming
Calcium water a loose compound with the haemoglobin (the red colouring matter) of the
Chloride red blood corpuscles.
to dry the The use of the oxygen and the presence of carbon dioxide may be ex-
air plained briefly as follows. The process of digestion converts our food
Cotton wool materials into compounds which are either soluble in water or easily
emulsified with it. The soluble compounds are absorbed into the blood as
the food passes through the small intestine. They are carried round by the
Iron nails Iron nails

II
Fio. 54.
To show thai iron will not rust in the presence of:
1, air alone; II, water alone.

(2) Exposure of iron to water separately. Boil about 350 cm 3 of

water rapidly in a beaker for at least half an hour. This will boil all
the air out of it. Put a few iron nails into a test-tube and fill it to the
brim with the boiled water. Press into the mouth of the test-tube a
rubber stopper carrying a glass tube and rubber tube as shown in Fio. 55.
Fig. 54, II. (Note that the glass tube must be flush with the bottom To show the presence of carbon dioxide in respired air.
186 A NEW CERTIFICATE CHEMISTRY
blood-stream and used either to replace wastage and maintain growth in
the body-tissues or to supply energy for movement of the body and to
maintain its temperature at about 98.4°F, a temperature usually consider-
ably higher than that of surrounding objects. This energy is supplied by
oxidation of the soluble products of digestion. Consider, for example, a
sugar. It is well known that if a sugar is thrown on to the fire it burns
vigorously, giving off heat, and forming, as products of combustion, carbon
dioxide and water. The same oxidation process, giving the same products,
occurs in the body, the oxygen being taken from its loose combination
with hemoglobin to oxidise the dissolved sugar. For a given quantity of
sugar oxidised, the same amount of heat is given out whether it is burnt
rapidly on the fire or oxidised more slowly in the body.
QHj.O, + 60, —* 6CO, + 6H.O; a definite quantity of heat liberated
This isthe source of the body's heat. The waste product, carbon dioxide,
is carried round in the blood (chiefly as bicarbonate) and is liberated as the
blood passes through the lungs, from which it is breathed into the air. The
breathing process of animals is similar.
It has already been pointed out that all common fuels give off carbon
dioxide when burnt. Living animals also discharge carbon dioxide as we
have just seen. There must obviously be some agency at work using up
these vast quantities of carbon dioxide and restoring the oxygen absorbed
from the air during combustion, for otherwise the composition of the air
would change appreciably.
Actually, the plant life of the world is at work restoring the balance. With
the help of energy from the sun and with chlorophyll (the green colouring
matter of leaves) as catalyst, plants are continually building up carbo-
hydrates (e.g., starch and sugar) from water and carbon dioxide of the air.
Carbon dioxide + water 4- energy —* starch + oxygen
Oxygen liberated and passes into the air. Notice that this process
is
(photosynthesis) is endothermic. The energy absorbed is released again when
carbohydrates are used as food and oxidised in the blood-stream to carbon
dioxide and water (see p. 187). It is obvious that the waste product, carbon
dioxide, breathed out by animals and given off by carbonaceous fuels, is
the raw material from which plants build up carbohydrates. The waste
product, oxygen, from the plant is the gas essential for animal breathing
and combustion of fuels. These opposing processes, at work together, keep
the composition of the air constant.
In addition to carrying on the above feeding process, plants also breathe
in the same way as animals, but, relatively, their breathing process is of
small account. On balance, a plant uses up carbon dioxide and liberates
oxygen. It may be mentioned that, biologically, the characteristic difference
between animals and plants is not connected with size or movement or
similar factors, but lies in the fact that plants build up (synthesise) complex
starchy food materials from the simple compounds, carbon dioxide and
water, while animals must have these complex materials available as food
and break them down by digestion into simpler substances.
Experiments illustrating the above brief outline will be found described
in any elementary text-book of biology.
Extraction of starch
Starch a carbohydrate, having a chemical formula of the type C x (H,0) v
is
— O
in this case, C,H 10 6 as the empirical formula. Production of starch by
,
STARCH 187
photosynthesis (above) and storage of the product is a plant's method of
providing a reserve of nutrition and energy, e.g., in seeds and tubers. To
extract starch, potatoes (for example) are pulped with water and the starch
is washed out. Sieving retains cellulose
and allows starch to pass; water is
then centrifuged away and the starch dried.
Starch has many uses. Wheat starch is the main constituent of bread in
Europe and America, and maize starch of cornflour. Potato starch is widely
consumed as food and other edible forms are sago, tapioca, rice and arrow-
root. Potato starch is used in the manufacture of glucose, dextrins and
starch syrup. Until recently starch was the main source of ethanol (alcohol)
by fermentation and a great quantity of alcoholic beverages is still pro-
duced this way, but industrial alcohol is now largely made from petroleum
products such as ethylene (p. 334).
When used as human food, starch is hydrolysed by enzyme action to
glucose which is utilised in three principal ways: for production of energy
by oxidation to carbon dioxide, for storage as fat and for storage as
glycogen, a compound which readily breaks down to glucose as the body
needs it.
Starch can be chemically hydrolysed in several successive stages. Cold,
dilute mineral acid converts it to soluble starch, which dissolves in hot
water and does not set to a paste on cooling. Dry heat (as in baking bread)
produces dextrins of the kind which colour and flavour bread crust or
toast and more complete hydrolysis produces glucose (a sugar).
Test for starch. Starch itself, and soluble starch, give a dark blue colora-
tion with iodine, which disappears on heating but reappears on cooling.
(The more complex dextrins produce a red colour with iodine but simpler
dextrins and glucose give no colour reaction with iodine.)
Conversion of starch to glucose
Starch is mixed with about 2\ times its weight of water and about 1%
of sulphuric acid is added. This mixture is heated under pressure for about
90 min, after which glucose solution is left.
(C,H 10O6). + «H a O - wC,H„0,
A slight excess of chalk is added to destroy the remaining acid and calcium
sulphate is filtered off. After decolorisation with charcoal and evaporation
under reduced pressure, glucose crystallises out after cooling and can be
separated.
Structure of the starch molecule
A starch molecule is produced by the combination of many molecules
of glucose, C( HitO( , with elimination of molecules of water. Since this
splitting out of H,0 molecules is classed as condensation and many mole-
cules of glucose are involved, starch can be called a condensation polymer of
glucose. For this purpose, glucose can be written as HO.C,H 10 4 .OH. O
Hydroxyl groups from a pair of different glucose molecules eliminate a
water molecule between them and this happens repeatedly to form a very
large linear molecule in the following way. Letting C( Hi,0, = X,
HO-X-olHTHOr-X— (H + HOr-X-OlH + HO|—X—OH ->
HO—X—O—X—O—X— O—X—OH + 3H 2
 188 A NEW CERTIFICATE CHEMISTRY QUESTIONS 189

Between 200 and 500 glucose molecules can group themselves together How would you find by experiment the percentage, by volume, of
9
in an actual starch molecule, giving a possible molecular weight in the are always present in the air?
oxv'een in the air? What other gases
region of 60000. If the chain-molecule formed remains straight, the
What is a physical change? Describe a simple laboratory experiment in
material is called amylose, but if a branched structure is formed with many
which some 'air' is obtained of different composition from the ordinary air
offshoots (usually about 20 glucose units long), the product is amylopectin.
as the result of a physical change.
(L.)
Various samples of starch have varying proportions of the two. Hydrolysis and function in plants.
10 State briefly the chemical nature of
starch its
with hot, dilute, sulphuric acid puts back the H,0 molecules and breaks prepare in the laboratory a
up the chain to single glucose molecules again. The two components of Given a sample of starch, how would you
chemical test by which
starch differ somewhat in behaviour with iodine. Amylose gives a blue reasonably pure solution of glucose from it? Give a
longer contains starch.
colour and amylopectin reddish purple. vou would demonstrate that this solution no
Glucose contains carbon, 40.0%, hydrogen, 6.7%, and
oxygen, 53.3%.
Show that its empirical formula is CH,0. If its molecular weight
is 180,

what is its molecular formula? (C = 12, O = 16, = 1.) H

QUESTIONS
1. What happens when
the following substances are exposed to the air:
Lead accumulator (reference from p. 152)
The lead accumulator is a secondary cell, i.e., it has to be 'charged'
(a) quicklime, (b) solid sodium hydroxide, (c) washing soda, and (rf)
rectified mains current) through it,
anhydrous calcium chloride? How would you confirm experimentally your by passage of direct current (usually
for use where required,
answer in one case? (N.U.J.B.) after which it will 'discharge' yielding direct current
e.g., in the electrical system of an
automobile. These processes of charge
2. What do you understand by the term combustion ? Give two examples
of combustion in which oxygen plays no part. Describe experiments which and discharge can be repeated many times.
illustrate the resemblance between the combustion of a candle and the The cathode and anode of the accumulator are both grids ot leaa-
alloy. At discharge, both grids carry a lead
sulphate filling. The
respiration process in an animal, giving sketches of any apparatus you antimony
electrolyte is sulphuric acid suitably diluted with water.
would use. (D.)
During charge, the following changes occur.
3. An ordinary paraffin candle consists of carbon and hydrogen in com-
At cathode At anode
bination. State what becomes of the candle when it burns in air, and
describe an experiment in support of your statement. Make a sketch of the fPb*+ + 2e- -> Pb fPb«+ + 2H .O - 2e~ -+ PbO, + 4H+
apparatus you would use to show that the weight of the products of com- 1504*- into solution \S0 4 *- into solution

bustion is greater than the weight of the candle consumed. (N.U.J.B.) That is, the cathode grid acquires a
filling of spongy leadmd the anode

4. Explain concisely the chemical meaning of the terms combustion

and gridone of lead(IV) oxide. Passage of ions into solution (from equations
a ~ to 4H+ increases the concentration
rusting. Describe the experiments you would make to
show what reactions above) in the proportion of 2S0 4
take place when iron rusts in moist air. (O. and C.) and density of the acid. At full charge, the E.M.F. is a little above 2 volts
-
5. When copper is heated in air, a black substance is formed. How and the acid density is 1.25 gem *. . .. «.,__,
following
would you prove that the copper had combined with another element to During discharge the cell yields electrical energy by the
form this new substance, and how could you determine what this element changes.
is? (N.U.J.B.) At cathode At anode
6. a green plant is placed in a closed volume of air in daylight, what
If Pb->Pb ,+ + 2e~ PbO, + 4H+ + 2e-— Pb'+ + 2H.O
changes would you expect to result in the composition of the air? How From solution, SO/ - . From solution, SO« ,_.
would you demonstrate that t hese changes occur ? To what do you attribute PbSO, deposits. PbSO, deposits.
them? (O. and C.) Electrons available from lead at the cathode pass round the
external
circuit performing the electrical work required and are absorbed at
7. (a) Give briefly three reasons for regarding the
air as a mixture and not a
compound. anode. Absorption of ions (4H+ 2S0 4 2 -) from the electrolyte decreases
:

(6) How would you determine the weight of oxygen in a given the concentration and density of the acid. The E.M.F. falls to 2 volts
volume of air? Sketch the apparatus you would use and show, soon after discharge begins and stays constant until it is almost complete,
using an imaginary case, how you would work out the calculation, then railing to 1.8 volts. At this point, recharging is required. {For the
(c) Describe briefly how you would determine the volume of oxygen Leclanchi cell, see p. 152)
in a sample of air confined over water in an eudiometer tube.
(N.U.J.B.)
8. Describe in detail how you would proceed in order to remove
com-
pletely the oxygen, carbon dioxide, and water-vapour from ordinary
air.
How would you prove that the residual gas was really free from these
substances? (L.)
 WATER 191

rain water from clean districts (which contains 0.0005% of solid

impurities) to sea-water, in which the impurities reach the compara-
tively high proportion of 3.6%. (In certain lakes the proportion of
solid matter is even higher.)

Chapter 15 Purification

A sample of pure water can be made from rain water, tap

fairly

water, or river waterby the process of distillation.

The impure water is placed in the distilling flask and is boiled (Fig.
Water and Solution
56). The steam comes off (together with gaseous impurities) whilst

[Thermometer
Water is essential to life

WATER is of fundamental importance to ail kinds of plants and

animals and therefore to man. It is of equal importance with the

air we breathe in maintaining the vital processes necessary to life and
growth, but since it is not everywhere available its provision has,
from the earliest times, limited the setting up of villages and towns
to the places where a water supply existed. Not only is water used
all over the world in vast quantities for drinking purposes, but it is
used in even greater quantities for washing, bleaching, dyeing,
raising steam to drive engines, and as a solvent in industrial processes
far too numerous to mention. It is the concern of the chemist to
ensure that a supply of water is maintained which is suitable for all
these purposes.
If the water is too soft (see p. 201) it will attack the lead of the pipes
in which it may be carried. If acids are present from decaying organic
matter, sufficient lead may be dissolved by the water to cause harm
to those who drink it. If the water supply for a town is too hard,
because of the high percentage of dissolved solid matter which it
contains, no firm will consider establishing a new industry there
Fig. 56.
because of the enormous extra expense which they will incur in
Distillation of impure water.
softening the water.
Purification plants used in swimming baths, by the use of chlorine, the solid impurities are left behind. The steam is condensed to water
keep the water comparatively free from the bacteria which carry
in the condenser. A
pure liquid distils at a constant temperature
many infectious diseases. The development of the high-pressure steam which is its boiling-point at the prevailing pressure (for water 100°C
boiler, for the driving of machinery of all kinds, would have been
at 760 mm). This behaviour is a recognised test for purity of a
impossible but for the solving of the problem of how to obtain water 218.
liquid. Tot fractional distillation, see p.
of a sufficiently high degree of purity for use in these boilers. The above
are a few samples of how Chemistry is of use in the service of man. Pure water
The preparation of perfectly pure water (or as near to perfectly
Occurrence of water
pure water as its unusual solvent powers will allow) is a matter of
Pure water does not exist in a natural state, but supplies of water much difficulty. It is prepared for conductivity experiments by as
are obtainableall over the world, varying in degrees of purity from many as twenty successive distillations from a pure tin or platinum
190
192 A NEW CERTIFICATE CHEMISTRY WATER 193

retort into a receiver which has been cleaned by having the purest drinking a little of the glass as well. It is true you need not get

water then obtainable kept in it for ten years! Potassium permangan- alarmed, for the amount is very small indeed, but for certain ex-
ate is added to the impure water in the earlier stages to oxidise periments ordinary glass vessels cannot be used as containers for
organic impurities. water because of this solvent effect.
Tap water can easily be shown to contain a considerable quantity
Properties
of both dissolved solids and gases by the following experiments.
Water is a clear colourless liquid with an insipid taste. It is usually
recognised in the laboratory by its capacity to turn anhydrous tap water contains dissolved solids
To show
copper sulphate (white) to a blue colour.
Filla large clean clock-glass with tap water and evaporate it down
CuSO« + 5Hj,0 -> CuSO.,.5H 2
to dryness on a steam-bath as shown in Fig. 57. On holding the glass
copper water hydratcd copper
sulphate sulphate (blue) up to the light or against a sheet of white paper, you will observe a
large number of concentric rings of solid matter left as the water
This test, of course, merely denotes the presence of water and not
the absence of everything else except water; e.g., a dilute solution of gradually evaporated.
sulphuric acid would turn anhydrous copper sulphate from white to
blue. PURE
water has the following properties: To show that tap water contains dissolved gases

(a) It freezes at 0°C. Filla flask with water and put in a few pieces of porous pot. Insert
(b) It boils at 100°C, when the barometer stands at 760 mm, and a two-holed rubber stopper to which are fitted a delivery-tube and
pure water will boil away completely with no change in temperature.
(c) Its maximum density is 1 g/cm* at 4°C.
(d) It is neutrarl to litmus.

Water as the universal solvent

There are few substances which do not dissolve in water to some

extent.Even when you drink your morning glass of water, you are
.Tap water

^flssa
Small paper-
wedge
Fio. 58.
To show tap water contains dissolved gases.

wwnnmtwirinnr&jiittc a short piece of glass tubing which can be closed by a rubber tube
and clip and attached to the tap in the initial stages (the end of the
delivery tube should not project beyond the surface of the stopper).
By attaching the small piece of glass tubing to the tap by means of a
rubber tube the whole apparatus (including the delivery-tube) is
filled with water (Fig. 58). As the water is heated, bubbles of gas
are
Appearance of clock-glass
after evaporation seen to rise and these will collect and be carried over into the burette.
Boil the water until no more gas is given off. The gas can be shown
Fia. 57. to differ from air in that its oxygen content is much higher, and the
To show tap water contains dissolved solids. gas boiled out will rekindle a glowing splint.
194 A NEW CERTIFICATE CHEMISTRY WATER 195

To determine the volume of oxygen in the air boiled out of water nitrate are ground together in a mortar,
because the average distance
•
Use in the last experiment a burette into which will fit the absorp- of the particles from one another is too great.

tion cup (G. Fowles) shown in Fig. 59. In the above cases the water acts as a medium in which the action
Fill the cup with crystals of takes place. It does not as a rule react with ihe substances. The
pyrogallic acid and add water chemical actions of water, however, as an oxide and as a hydroxide
4* to fill up the air spaces. (See producer are extensive.
Fig. 59.)Have ready a piece
Action of water on metals
of solid caustic soda (make
certain that it will be able to Attack
enter
r
v' a
I

water.
Woter level the burette), insert it f

into the burette and follow it

quickly with the absorption
Attack
cup. Invert the tube several
steam
times and release the cup under
water. Transfer the tube to a
deep gas-jar, lower it until the
. — —— - -/— - -^Caustic soda'stick levels are the same and inside
Do not attack
out, and note the volume of water or steam.
gas absorbed. The percentage
of oxygen in this air will be
Pyrogallol crystals more than 30%. By an examination of the electrochemical series it is easily shown
covered with water Value of these dissolved a degree varying with their position
that water attacks the metals to
gases to fish life. The oxygen
in the series.
of the air dissolves in water Potassium. Place a small piece of potassium on water in a large
1

to the extent of only 4 volumes

of oxygen in 100 volumes of Potassium

Fig. 59. water (i.e., 1 dm* of water

Absorption cup. contains only a maximum of
40 cm 3 [or 0.06 g] of oxygen).
Although amount is only very small it is of utmost impor-
this
tance to fish life. The fish (with a few exceptions) rely on this Fio. 60.
oxygen for breathing, in just the same way as we rely on the air Action of potassium on water.
around us.
dish (notice the silvery gleam of the unoxidised metal as it is cut
Chemical value of the solvent properties of water with a knife). The potassium melts to a silvery ball, darts about the
Use is made of this exceptional property to bring
in the laboratory water and a gas is given off (hydrogen) which burns spontaneously
into very close contact the particles of reacting substances. When the with a violet flame (the colour is due to the burning of small quantities
particles dissolve in water they have an opportunity for movement of potassium vapour) (Fig. 60).
which they do not have in the solid state. Under these circumstances 2K + 2H 2 -»- 2KOH + H 2
potassium water potassium hydrogen
many reactions take place which do not take place if the reactants are hydroxide
solids (see ionisation), e.g.,

AgNO a (aq) + 1
Under no circumstances should the piece of potassium be larger than a small
NaCl(aq) -»- AgCl(c) + NaNO a (aq)
pea, as the action is very vigorous. Stand well back from the dish as the
action
The above reaction will not take place if common salt and silver proceeds.
196 A NEW CERTIFICATE CHEMISTRY WATER 197

If a piece of red litmus is placed in the dish it will turn blue because of has boiled for a minute, remove
Hydroge r~\
the presence of potassium hydroxide, which an
is alkali. the Bunsen and let bubbling
Sodium. Perform the above experiment cease. The ribbon is lighted and
tydrogen with sodium The sodium melts to a plunged into the steam, the cork
silvery ball, but does not burn unless it is fitting into the neck of the flask.
restricted in movement. Effervescence The magnesium continues to
occurs, a gas is liberated, and if a light is burn, forming a white ash (mag-
applied burns with a yellow flame (the
it nesium oxide) which drops off
yellow colour is from the sodium). If the into the water. When the action
sodium is packed tightly into a sodium has ceased, remove the boiling-
spoon (see Fig. 61) the gas can be collected tube and apply it immediately
Fig. 61. and shown to be hydrogen. to a flame, when there will be an
Action of sodium 2Na + 2H O * 2NaOH + H, explosion due to the combination
a
on water. sodium water sodium hydrogen of the hydrogen produced with
hydroxide oxygen of the air which is not
completely displaced from the
Calcium. Drop a piece of calcium (a grey metal) into a dish of
tube.
water and invert over it a boiling-tube full
. of water. There is effervescence, and a gas The piece of litmus paper will,
H .

after a time, turn blue. The mag- Fig. 63.

V\ (hydrogen) is given off which explodes if
mixed with air and a flame is applied (Fig. nesium oxide is only slightly sol-
Action of burning magnesium on steam.
§ jfr l uble in water, but it will dissolve
"
62). The calcium dissolves, and if carbon
| sufficiently to turn litmus blue, showing the presence of a hydroxide.
dioxide is bubbled into a sample of this
CMaum solution (blow into it down a glass tube), Mg(c) + H.O(g) -»- MgO(c) + H 2(g)

M Fig. 62.
i
a milkiness due to a suspension of calcium
carbonate in water is obtained. The solution
is, in fact, lime-water, i.e., calcium
hydroxide (slaked lime) dissolved in water.
(N.B. The above experiment shows that steam contains both
oxygen and hydrogen.)

method (see Fig. 64)

Alternative
Action of calcium Blow a small hole in a hard-glass by applying a small
test-tube
on water. Ca + 2H O -> Ca(OH), +
s H, blowpipe flame until the tube is soft and blowing at the open end
calcium water calcium hydrogen
whilst the glass is being heated.
hydroxide Hydrogen bunts
on meeting alr^ Put a coil of 15 cm magnesium
Magnesium. This metal will not act appreciably on cold water but ribbon in the tube, add 2 or 3 cm
3

is attacked by boiling water. Steam vigorously attacks a piece of of water, insert the cork and clamp
lighted magnesium ribbon. The demonstration of the action of the apparatus by the cork at the
magnesium on steam is beset with the practical difficulty that the Hardalass angle shown (Fig. 64). Heat, gently
temperature is so high that if the burning magnesium comes into at first, with a Bunsen burner,
contact with any glass, cracking immediately ensues. The following keeping the latter moving to
apparatus overcomes this difficulty in a simple way. Bunsen mono" Co maintain an atmosphere of steam.
heat both water
A stout, very wide short-necked flask is partly filled with water and and magnesium Finally heat strongly when the
a piece of red litmus paper is dropped into the water and the water
Fig. 64. magnesium will burn and simul-
heated to boiling (Fig. 63). Meanwhile a piece of magnesium ribbon taneously the liberated hydrogen
is attached to the piece of apparatus by pulling the cork away from will burn as it meets the outside air.
the glass tube a little, and pushing the ribbon in parallel with the Zinc does not attack hot or cold water. If zinc is heated to redness
glass. Over the glass tube is placed a boiling-tube. When the water in a current of steam, hydrogen is formed.
198 A NEW CERTIFICATE CHEMISTRY WATBR 199

Zn + H,0 ->- ZnO + H, The above three hydroxides are soluble in water (slaked lime only
zinc slightly) and together with ammonium hydroxide form the common
oxide
alkalis.
Iron does not attack water (rusting takes place only when air is
Sulphur dioxide reacts readily with water to form sulphurous acid.
present as well) but is readily attacked by excess of steam at red heat.
This method is often used as a method of preparing hydrogen in S0 8 + H 0->-H
2 2 SO,
sulphurous
quantity (see p. 265). acid
3Fe + 4H 2
-> Fe,0 4 + 4H 2 Similarly, other acidic oxides form acids with water, e.g.,
iron
(red hot)
steam triferric
tetroxide
hydrogen S0 3 + H 0->-H
2 2 SO,
sulphur sulphuric
black oxide trioxide acid
of iron
The above reaction can be made to proceed in the reverse direction
2N0 2 + H 2 -> HNO, + HNO,
nitrogen nitrous nitric
by passing excess of hydrogen over heated black oxide of iron (see dioxide acid acid

p. 158). C0 2 + H 2 -»- HgCO,

carbon carbonic
Action of water on non-metals dioxide acid

Carbon attacks steam at a bright red heat, forming carbon mon- Action of water on chlorides. See Chlorides, p. 370.
oxide and hydrogen. Action of water on certain metallic carbides
C(c) + H 2 0(g) -> CO(g) +H 2 (g) Calcium and aluminium carbides react with water forming the
Chlorine acts on water to form hypochlorous acid. hydroxide of the metal and hydrocarbons.
Cl s + H 20-»-HOCl + HC1 CaC 2 + 2H 2
-> Ca(OH) a + C 2H 2
chlorine acetylene
water hypochlorous hydrochloric
acid acid Al t C, + 12H 2 -»- 4Al(OH) 3 + 3CH«
methane
Action of water on oxides
Composition of water
Potassium oxide is attacked by water with the formation of potas-
sium hydroxide. The results of experiments already performed indicate clearly that
K2 + H 0-»-2KOH
2
water contains hydrogen and oxygen. If hydrogen is burnt in oxygen
potassium water potassium or exploded with it, water is produced (p. 269) and nothing else
oxide hydroxide (p. 116). It remains to find thenumber of atoms of each element which
Sodium oxide is similarly attacked by water with the formation of is present in the molecule.
sodium hydroxide. Volume composition of steam. The experiment described on p. 116
Na.O + H 2 0-»-2NaOH
shows two volumes of steam to be formed from one volume of
sodium water sodium oxygen and two volumes of hydrogen. It follows that the formula for
oxide hydroxide
steam is H 20.
Calcium oxide (lime). Place a piece of quicklime in a dish and add Electrolysis of water. The above is the synthesis of water from its
water a few drops at a time. For a little while nothing is observed and elements whilst electrolysis is the analysis. On electrolysis of water
then water-vapour is seen to come off, whilst a hissing sound as the (see p. 145), it is found that the volume of hydrogen liberated is twice
water drops on indicates that the mass is becoming hot. It com- that of the oxygen liberated, thus confirming the above experiment.
mences to expand and crack, and finally crumbles to a powder,
slaked lime. Gravimetric composition of water
CaO + H2 -»• Ca(OH), Hydrogen was at first taken to be the standard (H 1) for the =
calcium water calcium determination of Atomic Weights. Now the first step in a deter-
oxide hydroxide
(lime)
mination of an atomic weight is usually a determination of the
 200 A NEW CERTIFICATE CHEMISTRY HARDNESS OF WATER 201

equivalent weight, and since many elements do not combine with or

hydrogen metal palladium. The hydrogen was expelled by
in the
displace hydrogen readily, their equivalents have been determined by
heating the palladium to redness.
finding the weight of the element which combined with the equivalent
of oxygen. Hence it
equivalent of oxygen.
is necessary to know with great accuracy the HARDNESS OF WATER
the earth's surface.
This is determined by passing purified hydrogen through several There are many types of natural water found on
U-tubes of calcium chloride to dry it, and then through a tube con- purest natural water, and if collected in a country
Rain water is the
the
taining pure dry copper oxide which is heated strongly. The latter districtcontains oxygen, nitrogen, carbon dioxide (dissolved as
tube and its contents are first weighed (Fig. 65). The water which the atmosphere) and only a small amount
rain drops pass through
passes over is collected in another set of calcium chloride tubes which of dissolved solids (0.0005%).
supplies are obtained, will
are weighed before and after the experiment. River water, from which many domestic
obviously contain the same gaseous impurities
and also any solids
CuO + H, — >- Cu + H 2
passed over the soil. The amount
copper hydrogen copper water which the water has dissolved as it
oxide depend, therefore, on the type of soil over
and kind of impurity will
The loss in weight of the tube containing the copper oxide gives the water runs. If the water runs over impervious material
which the
pure as rain water.
weight of oxygen, and the difference between the increase in weight such as granite, the river water may be nearly as
the large river from
of the absorption apparatus and the weight of oxygen gives the weight In actual practice many springs and rivulets feed
of hydrogen which has combined with the oxygen to form water. which a town's supply is obtained, and hence the impurities are often
the same as those of spring water.
Pure dry
Black Copper
A J
Absorption oF Spring water is water which has made its way downwards thiough
Oxide water apparatus
Hydrogen •

the soil and contains solid impurities.

eventually
Sea-water is the reservoir into which all the impurities
is usually high (3.6%).
go, and hence the solid content of sea-water
Calcium Chloride The solids which are found in the natural waters are mainly the
tube to prevent
entry of sulphates and bicarbonates (hydrogen carbonates) of calcium and
moisture Into magnesium together with smaller amounts of sodium chloride,
absorption
apparatus silicates, nitrates, ammonium as well as the gaseous impurities
salts,

already mentioned as being present in rain water, i.e., oxygen,

Calcium Chloride
to absorb water nitrogen and carbon dioxide.
Loss in weight gives weight of oxygen Gain in weight gives weight of Of the solid impurities the most important are calcium sulphate
which has combined with the hydrogen water formed and calcium bicarbonate (hydrogen carbonate),
Difference gives weight of hydrogen
Calcium sulphate is present because many rocks and soils
Fig. 65. contain gypsum (CaS0 4 .2H gO) which is slightly soluble in
Gravimetric composition of water. water (1 : 500) and hence some of it dissolves in any water
with which it comes in contact.
By an experiment involving the combination of the elements Calcium hydrogen carbonate is present because water
themselves it was found that which contains carbon dioxide is capable of dissolving small
quantities of limestone or chalk (which is found in large
1 g of hydrogen combined with 7.9396 g of oxygen
quantities in some soils and in small quantities in practically
This accurate figure was obtained by Morley (1890-5), who suc-
all soils).
ceeded in weighing the hydrogen, oxygen and also the water formed.
The latter, of course, introduces a check on any error made. The diffi- CaCO, + H tO + C0 2
-»• Ca(HC0 3 ),
limestone water carbon calcium hydrogen
culty of weighing a volume of hydrogen (because of the very small (insoluble) dioxide carbonate
weight of even a large volume) was overcome by absorbing the (slightly soluble)
 .

202 A NEW CERTIFICATE CHEMISTRY HARDNBSS OF WATER 203

It will be obvious that all the more soluble substances calcium stearate (which appears as a 'curd'), the latter being
present on the surface of the earth were washed away in the insoluble, e.g.,
course of past ages. 2NaSt + CaS0 4 -* Na 2 S0 4 + CaSt 2
sodium calcium
Definition. A hard water is one which will not readily form a lather sodium calcium
sulphate sulphate stearate
stearate
with soap. (soluble) (soluble) (soluble) (insoluble)

The nature and method of manufacture of soap
Soap is the sodium salt of an organic1 acid. One of the commonest
soaps is the sodium salt of stearic acid, C 17 H MCOi,H, and has the
formula, C^HjaCOjNa, sodium stearate. It is important to notice
that, for all its complex formula, soap is of exactly the same chemical
Until the whole of the calcium compound has been acted
upon by the soap, none of the latter can form a lather.
Thus, with a hard water, a large amount of soap is used to
precipitate and remove the calcium, and only a small extra
amount to cause a lather.

nature as common salt, NaCl. Both are sodium salts of acids. The In this way the valuable stearate group, which loosens the dirt, is

complex group, C^HajCOj— , of sodium stearate corresponds to the lost completely, since it would be just as useful to try to wash with
CI of sodium chloride. For convenience, the formula of sodium insoluble calcium stearate as any other substance insoluble in water,
stearate is often written NaSt, the St being used as a substitute for the e.g.,marble, or iron.
stearate group, C^HsjCOj — This is not the only reason why hardness must be removed. Where
Soap manufactured by heating vegetable oils (such as palm oil
is water is used for boilers, certain of these solid substances (calcium
or olive or animal fats with caustic soda solution. The oils or
oil) sulphate and magnesium silicate being the worst offenders) are left
fats are compounds formed from glycerine and certain complex behind as scale on the inside of the pipes of the boiler as the water is
organic acids, such as stearic acid, mentioned above. The caustic evaporated off. As this scale increases in thickness, the bore of the
soda liberates glycerine from the fat and forms the sodium salt of pipe becomes smaller, and the walls of which the pipes are made
the acid, which is the soap. (Caustic soda is sodium hydroxide.) become heated to a higher temperature than is normal, causing the
Fat or oil + caustic soda —> soap + glycerine pipes to weaken and finally burst.

Soap manufactured by steam-heating the fat and caustic soda solu-

is Other detergents have been introduced recently to replace soap in
tion in large pans. Common salt is added later and assists in the domestic and laundry work. A
typical detergent is made from a

separation of the soap which, when cool, sets as a hard cake on the complex alkene, i.e., a hydrocarbon of the type, C„H 2 „, where n is
surface of the liquid. It is removed and purified, dyes and perfumes between 12 and 20. The alkene is first sulphonated by concentrated
being added to produce toilet soaps. sulphuric acid; the sulphonate is then converted to its sodium salt
The manufacturing process can be illustrated in the laboratory, by sodium hydroxide solution. The sodium salt is the detergent. An
using mutton fat or lard. Put the lard into an evaporating dish and example is the following.
add to it a solution of caustic soda to which methylated spirit has C„H„ + H 2S0 4 -»- C 16H 3I .S0 4 H
been added to quicken the action. Heat the dish on a steam-bath. C MH 3l .S0 4 H + NaOH -> C 15 H 31 .S0 4 Na + H,0
When all the liquid has evaporated off, a yellowish solid will be left.
This detergent resembles sodium stearate (soap) in possessing a long
It is impure soap.
The soap cleanses by dissolving in the water, loosening the particles
fat-soluble carbon chain, Ci 6 3I H —
and a water-soluble end-group,
,

of dirt, and the whole (soap, water and dirt) can then be washed
— SO«Na.
Detergents of this kind have two advantages over soap; they are
away.
more soluble in water and are not affected by hardness in water. This
Cause of hardness is because the calcium salt of the detergent is
soluble in water whereas
insoluble. (See following sections.)
Now if there happens to be a calcium compound dis- calcium stearate is
solved in the water, the soap is precipitated in the form of
Removal of hardness
1
An organic compound isa compound of carbon. The chemistry of carbon
Distillation will remove all solid matter. This method is, as a rule,
is so complex that it is convenient to treat it separately from that of other
elements as 'organic chemistry'. far too costly to be employed.
204 A NEW CERTIFICATE CHEMISTRY HARDNESS OF WATER 205

Many high-pressure boilers supply steam to drive turbines, and the (1) To a piece of
the stalactite on a watch-glass, add a few drops
steam which comes from the turbines condensed to water, which is
is
of pure concentrated hydrochloric acid. Take up a
little of the mix-

actually distilled water. In some works, the water is fed back again platinum wire (sealed into the end of a glass tube to act
ture on a
into the boiler and small amounts of distilled water artificially pre- handle). Put the wire into the lower half of a Bunsen flame. A brick-
as
pared are added to make up the losses which are inevitable.
red coloration shows calcium present. (At first, the yellow flame of
Removal of calcium as calcium carbonate (chalk). Many of sodium may interfere, because sodium compounds are very common
themethods of rendering a hard water soft have as their impurities.)
object the conversion of a soluble calcium salt into the in- (2) Put two or three small pieces of stalactite into a narrow test-
soluble carbonate. In this way the calcium is removed, since tube and add dilute hydrochloric acid. Effervescence will occur. If the
will show a
the calcium carbonate, being insoluble, takes no further gas is passed into lime-water and the liquid is shaken, it
part in the reaction. An insoluble calcium salt cannot cause white turbidity. That is, carbon dioxide is evolved, proving the test
hardness. material to be a carbonate. (A hydrogen carbonate also gives off
carbon dioxide with this acid, but only two common hydrogen car-
Temporary hardness
bonates exist as solid in ordinary conditions— NaHC0 3 and
Hardness which is due to the presence of calcium hydrogen car- KHC0 3 .)
bonate can be removed by heating the water to boiling for a few
C(V" + 2H + -»- H O + CO a a
minutes. Heat decomposes the calcium hydrogen carbonate into
That is, the stalactite contains calcium carbonate, probably slightly
calcium carbonate (chalk) and carbon dioxide is expelled.
impure.
Ca(HC0 3 3 -> CaC0 3 +
) H 2 + CO, In cross-section, stalactites usually show a ring structure similar
calcium calcium water carbon summer rate of
hydrogen carbonate carbonate dioxide to that of a tree trunk. This occurs because the
(slightly soluble) (insoluble) deposition of chalk is more rapid than the winter rate, 'emperature
Because it can be removed merely by boiling, the name 'temporary' being lower in winter.
isgiven to this type of hardness. This method would be expensive on Removal of temporary hardness by addition of slaked lime
the large scale.
Temporary hardness can be removed by the addition of the cal-
Furring of kettles culated quantity of slaked lime (excess of lime would cause hardness
In a district where the water contains calcium hydrogen carbonate on its own account). The amount of lime is calculated from a know-
reservoir
become coated with a layer of calcium carbonate
the insides of kettles ledge of the hardness of the water and of the capacity of the
caused by the decomposition of the hydrogen carbonate according (Clark's method).
to the equation shown above. Ca(OH) 3 + Ca(HCO s) 2
-»- 2CaC0 3 + 2H,0
slaked lime calcium calcium water
Stalagmites and stalactites (slightly hydrogen carbonate
soluble) carbonate (insoluble)
These of almost pure calcium carbonate are made by water
pillars
(slightly soluble)
containing dissolved calcium hydrogen carbonate dripping from the
roof on to the floor of a cavern. Some of the calcium hydrogen car-
A third method of removal of temporary hardness is to add sodium
carbonate. (Permanent hardness is also removed at the same time.)
bonate decomposes, giving off carbon dioxide into the atmosphere of
the cave, and depositing calcium carbonate a little at a time on the Na,C0 3 + Ca(HC0 3),->- 2NaHC0 3 + CaCO s \
roof and floor. This deposition causes a stalactite to grow downwards Permanent hardness
from the top of the cave and a stalagmite to grow upwards from the
This due mainly to the presence of dissolved calcium sulphate,
is
floor of the cave, until after a time the two meet. The growth
which cannot be decomposed by boiling, and hence the name 'per-
varies very much from small fractions of a cm to 100 cm or more
manent' is given to this type of hardness.
per year. addition of washing soda crystals
It is most easily removed by the
If a sample of stalactite is available, its chemical nature can be
to the water, when a precipitate of insoluble calcium carbonate is
demonstrated by the tests given below.
thrown down and thus prevents the calcium from interfering.
 206 A NEW CERTIFICATE CHEMISTRY HARDNESS OF WATER 207

(You should make yourself quite certain of the reason why soluble water, you need not proceed further. The water is hard. Having
calcium sulphate can cause hardness, whereas insoluble calcium obtained the result for distilled water perform the following ex-
carbonate cannot. See p. 204.) periments.
CaSO, + Na,C0 3 * CaC0 + Na,SO. To show hard water. Take 25
that boiling softens temporarily cm 3 of
3
calcium sodium calcium the temporarily hard water made as indicated above and titrate
sulphate carbonate carbonate against soap solution. Notice the curd which forms.
(soluble) (insoluble)
CatHCOj), + 2NaSt-> CaSt, + 2NaHC0 3
calcium
PRACTICAL DETERMINATION stcarate
OF APPROXIMATE DEGREE OF HARDNESS (curd)

AND ILLUSTRATION OF THE ABOVE FACTS Take another 25 cm 3 and heat

to boiling on a tripod and gauze.
Notice that a milkiness appears (chalk). Cool. Titrate against soap
To make temporarily hard water
solution again and note your result when a lather is obtained which
Bubble carbon dioxide into lime-water in a flask for about 20 remains unbroken for 2 minutes.
minutes. The precipitate at first formed will have dissolved to form a Ca(HC0 3),-»- CaCO a + H,0 + CO,
temporarily hard water.
To show that washing soda crystals soften permanently hard water
Ca(OH), + CO,-)- CaCO, + H O a
Titrate 25 cm 3
of the permanently hard water and record your
lime- carbon calcium water
water dioxide carbonate result. Take another 25 cm3 of
the hard water, add a few crystals of
CaC0 3 + H,0 + CO, -> Ca(HC0 3 )a
washing soda, and shake until they dissolve. Again you will notice a
calcium water carbon calcium turbidity due to a precipitate of chalk.
carbonate dioxide hydrogen
carbonate Na,CO s + CaS0 4
-»• Na,SO« + CaCO, J
To make permanently hard water. Add a little gypsum or anhydrous Titrate again and notice your results. They should speak for them-
calcium sulphate to water in a flask. Shake and
allow to stand, selves. A typical set of results is given here.
decant olTthe clear liquid; you will find it will be Amount of soap solution
permanently hard
water. necessary to produce a
lather to last unbroken
To make a soap solution. Scrape shavings off a tablet of pure for two minutes.
Castile
soap. Weigh out about 6 g of shavings and add to 25 cm* distilled water
about 100 3
cm of
methylated spirit in a beaker on a water bath. Warm and stir. When 2nd reading 3.0 cm 2.0 cm'
dissolved, transfer to a 1st reading 1.0 cm :}
litre flask and add water to make up about
one litre. Shake and allow to stand. 25 cm' temporarily hard water
2nd reading 33.0 cm'\
N.B. Since the composition of soap is variable the 30.0 cm'
above solution 1st reading 3.0 cm*/
need not be made up with great accuracy, nor are
the readings to be 25 cm* temporarily hard water
taken as a mathematical comparison of hardness. after boiling
In these experi-
ments the hardness of various waters is being compared. 2nd reading 40.0 cm'\ 7.0 cm'
Fill a burette with the soap solution and place 25 cm 3 1st reading 33.0 cm'/
of distilled
water by means of a pipette into a conical flask. 25 cm' permanently hard water
Run in 1 cm 3 of the 2nd reading 31.0 cm'\
soap solution at a time and, between additions, cork 30.0 cm'
up the flask and 1st reading 1 .0 cm*/

shake. When a lather is obtained, which persists

unbroken for two 25 cm' permanently hard water to
minutes, the titration is completed. You will which washing soda was
easily see the difference
between a 'curd' (which is formed when soap solution added
is run into a
hard water) and a lather, as the former breaks very quickly 2nd reading 36.0 cm 3 \ 5.0 cm'
and the 1st reading 31.0 cm*/
latter consists of many tiny bubbles which
reflect the light from the 1
Indicates no lather produced. No more soap solution was added— the water
windows. When you have run 30 cm 3 of soap solution
into a hard is extremely hard.
208 A NEW CERTIFICATE CHEMISTRY SOLUTION 209
Pcnnut it method of softening water
These contain water of These do not contain water
The above methods of softening water and adding
(i.e., boiling crystallisation of crystallisation
'soda') are used mainly in the home for softening small amounts of
water. In the treatment of larger supplies of water (but not so large as Sodium carbonate crystals Sodium chloride
to be treated by the lime method) the permutit process is used. Many (Na 2 CO a .10H 2 O) NaCl
'water softeners' sold for domestic use work on this principle. Sodium sulphate crystals Potassium permanganate
Permutit is a complex substance (hydrated sodium aluminium (Na a SO 4 .10H 2O) KMn0 4
but we can regard it as Na 2 Y (Y
silicates) =
Al„Si 2 g .xH 2 0). O When Copper sulphate crystals Potassium nitrate
a dissolved calcium salt runs over it, ion-exchange occurs. (CuS0 4 .5H 20) KNO a
(Na + Y*- )8 Ca 2, + S(V-- Ca^Y*- 2-
+ (Na+),S0 4 Iron(ll) sulphate crystals Ammonium sulphate
insolublc (FeS0 4 .7H 2 0) (NH^SO,
The sodium permutit will finally become a calcium permutit, and it
can be made fresh again by running concentrated brine over it and SOLUTION
washing away the soluble calcium chloride formed.
Many solids possess the property of dissolving in water. For in-
CaY + 2NaCl -> Na,Y + CaCl, stance, if small crystals of copper sulphate (crush
we shake up a few
them in a mortar first) with water in a test-tube, the water will turn
blue and the crystals will finally disappear.
The particles of copper sulphate in the solution must be very small,
for we cannot see them with the naked eye, nor even with the most
powerful microscope made. Furthermore, they will pass through the
WATER OF CRYSTALLISATION pores of a filter-paper with ease. The solution (as this mixture is
called) of copper sulphate in water is uniform in blue colour and in
Place a few crystals of copper(II) sulphate in a test-tube and heat
composition (after stirring) and, in a sealed tube, remains so in-
gently.There will be a copious evolution of water-vapour (which will
definitely. In general, to produce such a solution, the ordered crystal
condense and run back and crack the tube if the mouth of the tube is
lattice of the solid (the solute) built up from positive and negative
not held lower than the bottom). The colour and shape of the crystals
will disappear, and in place of blue crystals of hydrated copper sul-
ions (see NaCl, p. 371) or from molecules (see I t p. 75), must first
,

phate, you will observe a white powdery mass of anhydrous copper be broken down so that its particles can diffuse between the mole-
cules of the liquid (the solvent) and move among them. Since the
sulphate.
on each
particles in the solid lattice exercise electrical attraction
CuS0 4 .5H 2 — >- CuS0 4 + 5H,0 other, energy must be supplied to separate them. This energy is
If water is slowly added to the white, anhydrous powder, hissing is
taken from the heat energy of the liquid; consequently, there is
heard and steam is evolved, showing that heat is generated. A blue
usually a fall of temperature as a solid dissolves in water. If, how-
solid is left. This liberation of heat energy occurs because the an-
ever, some form of chemical action occurs at the same time, e.g.,
hydrous copper sulphate is hydrated by the water and this is a
hydration of ions, this action may liberate enough heat to cause an
chemical action, i.e., combination of H a O molecules with the ions
overall rise in temperature, e.g., when anhydrous copper sulphate
of the salt. The heat generated is called heat of hydration. The
is dissolved in water.
reaction shown in the above equation is reversed.
Liquids other than water may act as solvents, e.g., chloroform,
Water of crystallisation is necessary to the crystalline shape of
carbon tetrachloride and carbon disulphide. These liquids, and many
some crystals, and is that definite amount of water with which the number of
others, are covalent compounds and dissolve a great
substance is associated on crystallising out from an aqueous solution. covalent solids, e.g., chloroform dissolves iodine, carbon disulphide
The crystals cannot form without the presence of water
in these cases + -
dissolves sulphur. Ionic compounds, e.g., Na Cl , do not usually
with which to form a loose compound. It is sometimes termed 'water
dissolve in covalent solvents but a great many are soluble in water,
of hydration'.
in which their ions can dissociate.
210 A NEW CERTIFICATE CHEMISTRY SOLUTION 211

To obtain the solute from a solution

Muddy is a typical suspension. The mud would settle after a
water
Into a porcelain evaporating dish pour a solution of common salt time undisturbed,
if left leaving a brown residue on the bottom of the
in water, and heat the contents on a tripod and gauze. Water-vapour containing vessel and clear water above. The particles of mud would
will be seen to come off and finally there will be left a white solid, be retained by a filter-paper whilst the water (and any solids in
common salt. solution) would pass through.
This method can be used to purify rock salt, since earthy impurities
and dirt will not dissolve and can be removed by filtration. Saturated solution
If we add half a gram of sodium chloride to 100 g of water in a

To obtain the solvent from a solution beaker the salt will dissolve. We could go on for a time adding salt
half a gram at a time and, by stirring vigorously after each addi-
If we could catch the water-vapour coming off in the previous
tion, bring about solution of the sodium chloride, but with increasing
experiment and cool we could recover the water free from common
it,
difficulty. Finally, there would come a time when no more sodium
salt, since the solid does not come off with the vapour. The method
chloride would dissolve at that particular temperature, and, no matter
of catching the vapour and cooling it is called condensation and the
how long we left it or how vigorously we stirred, no more sodium
apparatus employed is a distilling flask, condenser and receiver (see
chloride would dissolve. The solution then said to be saturated with
is
p. 191). The condenser consists of a long tube surrounded by a
sodium chloride at the particular temperature.
wider tube through which water can flow, to cool the vapours and
Definition. A saturated solution of a solute at a particular temperature
convert them into a liquid again. The whole process of boiling off
is one which contains as much solute as it can dissolve at that tem-
the liquid as vapour and then cooling it again so that it is received as
perature, in the presence of the crystals of the solute.
liquid in another vessel is called distillation. The product obtained
The concentration of a saturated solution varies with the solute,
here is called 'distilled water'. It is free from dissolved solids but may
the solvent and also with the temperature. Thus sulphur is almost
contain gases in solution. It has a 'flat' taste which makes it un-
insoluble in water yet readily dissolves in carbon disulphide and a
palatable. Distilled water is used in electric accumulators because
rise in temperature will cause more to dissolve.
the solids present in ordinary tap-water are injurious to the plates.
This is generally true for solids; for example, nitre is at least seven
times more soluble in water at 80°C than it is in water at 10°C.
Chemical solution
This a term often employed to indicate the apparent solution of
is
Determination of solubility
a solute in a solvent, together with chemical action. For example, zinc To give a quantitative meaning to solubility, it is necessary to fix

appears to dissolve in dilute sulphuric acid and neither zinc nor dilute the amount of the solvent and to state the temperature under con-
sulphuric acid can be recovered by evaporation or distillation, since sideration. The amount of solvent is usually fixed at 100 g.
the solid residue on evaporation would be zinc sulphate. Actually the Definition. The solubility of a solute in a solvent at a particular tem-
processes of chemical action and solvent action follow one another. perature is the number of grams of the solute necessary to saturate 100 g
The zinc attacks the acid to form zinc sulphate, which then dissolves of the solvent at that temperature.
in the water present. It denotes a limit, that is, the maximum amount which can normally
be held in solution. Solubility is also sometimes expressed in grams
Suspension of solute per litre of solution at a given temperature.
The above properties of a solution help us to differentiate between To determine the solubility of potassium nitrate in water at the tem-
a solution and a suspension. A solid is said to be in suspension in a
perature of the laboratory
liquid when small particles of it are contained in the liquid but are not
This determination must be carried out in two stages. It is first
dissolved in it.
necessary to prepare a saturated potassium nitrate solution at labora-
If the mixture is left undisturbed the solid particles will tory temperature and then to find the proportions of potassium
slowly settle to the bottom of the containing vessel, leaving and water in it.
nitrate
the pure liquid above them. To make the saturated solution. The rate of solution of a solid in
 SOLUTION 213
212 A NEW CERTIFICATE CHEMISTRY
That is, solubility of potassium nitrate is 25.0 g per 100 g of water at
cold water is generally so slow thatalmost impossible to obtain a
it is
15°C.
saturated solution of it in a reasonable time by merely shaking the
Generally, increase in temperature increases the solubility of a
solid with the water. The quicker and more certain way is to crystal-
solute in water. This is because most solutes dissolve in water with
lise from a warm solution by cooling.
absorption of heat. So, if a solution and solid crystals of the solute
Half fill a boiling-tube with water and dissolve in it some potassium
are in equilibrium at a certain temperature and the mixture is then
nitrate. Warm and shake well. Pour off a small sample into a test-tube
heated, the system will alter so as to tend to lower the temperature
and cool it under the tap. If no crystals appear, return the sample
again (Le Chatelier's Principle, p. 156). That is, more crystals will
to the boiling-tube and add more nitre. Test another sample
dissolve because their dissolution absorbs heat.
and continue in this way till a sample gives crystals. Then cool the
By finding the solubilities of a solute at varying temperatures a
whole solution. When the crystals have separated and the solution is
graph can be plotted to show how the solubility alters with increase
quite cold, take the temperature of it. Then filter it through a dry
of temperature, with many interesting results. This is called a solu-
filter-paper and funnel into a dry receiver to avoid diluting it. The
bility curve of the solute.
filtrate is a saturated solution of potassium nitrate at the observed
temperature.
To obtain the solubility of potassium nitrate, using this solution. To determine the solubility of potassium nitrate at S0°C
Weigh a clean dry dish and add some of the saturated solution to it. This is the method employed to determine the solubility at any
Weigh again. Once having weighed be careful not to lose any portion temperature above laboratory temperature. At these higher tempera-
of the solution. Place the dish on a steam bath (p. 192), and evaporate tures, the rate of solution of the potassium nitrate is greatly increased,
until the potassium nitrate is left quite dry. (The dish on a gauze may and a saturated solution may be made directly.
be warmed very gently over the Bunsen flame for a few minutes to
complete the removal of water.) Allow the dish to cool and weigh it.
Calculate the weight in grams of the potassium nitrate which would
have dissolved in 100 g of water as in the following calculation.
Stirrer
Alternative method of evaporation to dryness. The following method
is quicker than the one suggested above with little loss of accuracy if

carefully performed. Weigh a dish (75 mm

diameter is suitable) with
a clock-glass to fit over it. Weigh again, having added some saturated
solution of potassium nitrate and replaced the clock-glass. Evaporate
to dryness over a medium flame increasing the size of the flame
towards the end. Do not heat the solid sufficiently strongly to decom- Solid Water
Potassium
pose it. Allow to cool and weigh.
Nitrate

Weighings
Weight of dish = 14.32 g (a)
Weight of dish and solution = 35.70 g (o)
Weight of dish and potassium nitrate = 18.60 g (c)
Temperature of saturated solution = 15°C

Hence:
17.10 g (b — of water dissolve 4.28 g (c
c) —
a) of potassium nitrate
4 28
so, 100 g of water dissolve -^-— x 100 g of potassium nitrate
Fio. 66.
Solubility of potassium nitrate at 50 'C
= 25.0g
214 A NEW CERTIFICATE CHEMISTRY SOLUTION
Crush some crystals of potassium nitrate in a mortar, place some
of them in a boiling-tube and add a little water (to make the tube
about half-full). Put the boiling-tube in a beaker of water and warm
the latter up to a temperature of about 55°C (Fig. 66). Whilst warm-
ing the solution keep adding potassium nitrate crystals to the boiling-
tube, and stir all the time. Add potassium nitrate until some remains
undissolved at the bottom of the tube. Remove the flame when the
Solubility k
temperature, as read by the thermometer, reaches 55°C, and allow in grams
the apparatus to cool, stirring all the whileand always maintaining solute per
100 g jo
some undissolved potassium bottom of the tube. Just
nitrate at the water
before the temperature falls to 50°C, remove the stirrer, allow the
10
solid potassium nitrate to settle, and put the dry thermometer into
the potassium nitrate solution. When the temperature is exactly 50°C,
rapidly decant a of the saturated solution into a weighed dish,
little

leaving all solid potassium nitrate behind. Weigh the dish again and
evaporate to dryness as in the previous experiment. Calculate the
zo 30 40 bo si 70 ioo"e
weight of potassium nitrate dissolved in 100 g of water at 50°C in a
Fio. 67.
similar way.
Solubility curves of a few common substances.
By repeating the experiment at varying temperatures several values
can be obtained from which a curve can be plotted. On p. 215 is a For which salt does the solubility increase most rapidly with rise
(a)
table of values obtained in this way. Plot the graph on squared paper. in temperature?
The following figures were actually obtained by a middle school (b) Given a mixture of equal weights of potassium chlorate and
form. (The figures in brackets are the accepted accurate values.) potassium chloride, how would you obtain some pure chlorate?
(c) For which salt is there a decrease in solubility with increase in
temperature?
Temperature ll°C 50"C 57°C

/23.6 g 84g 102 g Super-saturation

g KNO, per
100 g water
|
L20 g)
(85 g) (106 g) Fill a 150 X 25 mm boiling-tube
to a depth of about 25 with mm
water, then up with crystals of 'hypo', sodium thiosulphate,
fill it

NajS 2 3 .5H 20. Heat the tube gently and shake until the crystals
Alternative method (using any substance which does not exhibit are all dissolved. Holding the boiling-tube quite still, cool the solution
supersaturation).
Weigh 4.5 g of potassium chlorate into a boiling-tube and run in Seeding"
10 cm 3 (g) of water from a burette. Warm until dissolved, remove /crystals
from the flame, insert a thermometer and allow to cool, stirring with
the thermometer. Note the temperature at which crystals appear. No crystals 's spreading
-downwards after
This be the temperature at which the solubility is 45 g. Add a
will Seeding Seeding
further 10 cm 3 of water and repeat the experiment. Continue the
addition, determining the temperature at which the solution is just ^Hypo"
saturated until 60 cm 3 of water have been added. Construct the graph.
(i)
sortition

m GO
Graph of
Look
solubilities

at the accompanying graph of the solubilities of a few com-

^ \a&i
Fig. 68.
mon salts. (Fig. 67.) Answer the following questions. Super-saturation.
216 A NEW CERTIFICATE CHEMISTRY DETERMINATION OF MELTING POINT 217
under the tap. Even when the solution is quite cold, no crystals separ-
Effect of dissolved substances on the freezing-point of solutions
ate (Fig. 68, i). Now select a single
pin-head size crystal of 'hypo' and
Water, if pure, freezes at 0°C, but if it contains some dissolved
drop it into the solution. At once, white crystals separate, growing
substance, it is found no longer freezes at 0°C, but
that the solution
slowly downwards through the solution and starting from the
at a lower temperature. It is also found that equal small additional
added crystal as centre (Fig. 68, ii). The contents of the boiling-tube
quantities of the dissolved solid cause equal depressions of the freez-
become almost a solid mass of 'hypo' crystals and only a very little
ing-point. Hence, the depression of the freezing-point of a solvent is
solution can be poured off. Note the rise of temperature as the
proportional to the mass of a substance dissolved in a given mass of
crystals separate.
the solvent for dilute solutions at constant pressure.
After the crystals have separated, the solution left must be still
saturated with 'hypo'. Before they separated, it must have been 'more Determination of melting-point
than saturated', or 'super-saturated', as it is called.
The melting-point of a solid (between, say, room temperature and
Definition. A solution is said to be super-saturated when it contains in
150 C) can be determined as in Fig. 69. A thin glass melting-point
o

solution more of the solute than it can hold at that temperature in the
presence of the crystals of the solute. q
It is important to notice that 'super-saturated' solutions are in an Thermometer
unstable condition. They can only be obtained to any marked extent:
(a) From a few compounds, for example: Glauber's salt
Na.SO^.lOHjO, 'hypo', Na 2 S 3 3 .5H tO.
(b) By excluding all dust. The dust particles might act as centres
of crystallisation,
(c) By cooling the solution slowly. 'Hypo' is exceptional in giving
a super-saturated solution when cooled quickly.
(</)

A
By avoiding all shaking or disturbance of the solution.
solution cannot be super-saturated
the solute.
if in contact with crystals of
h
Effect of dissolved solids on the boiling-point of a solution
Melting-point
3
Put about 200 cm 3 of water into a distilling flask (500 cm ) fitted tube
with a sensitive thermometer, which should read to tenths of a degree.
Add a few pieces of porous pot, clamp the flask at a suitable height
and heat the water to boiling-point and notice at what temperature cone, sulphuric Test material
the water boils. Add a weighed amount of sodium chloride, say 5 g
acid or glycerol-
and again determine the boiling-point. Repeat this experiment, adding
exactly 5 g of salt each time and noting the boiling-point after each
addition.

Specimen readings
C
Temperature of boiling water 99.7 C Fio. 69.
With 5 g of NaCI added 100.2°C Determination of melting-point.
„ 10 g 100.7°C
tube about 4 cm long (which can be drawn out from ordinary glass
„ 15 g „ „ „ 101 2°C
tubing) is touched into a Bunsen flame to seal one end. When it has
From these figures, elevation of boiling-point is proportional to cooled, a little of the finely powdered solid, e.g., naphthalene or
concentration (if solutions remain dilute and at constant pressure). benzoic acid, is scooped into the open end and tapped down to the
218 A NEW CERTIFICATE CHBMISTRY WATER OF CRYSTALLISATION 219

bottom of the tube to make a 2-3 mm

layer. The tube will adhere to ascending vapour can condense. This produces a succession of liquid
the thermometer by the surface tension effect of the liquid in the films in which, as the column is ascended, there is an increasing con-
flask and the test material should be as close as possible to the ther- centration of the more volatile liquid (of lower boiling-point). Ascend-
mometer bulb. The flask is gently heated and the melting-point tube ing vapour comes into approximate equilibrium with these liquid
is carefully watched. At a certain point, the solid will be seen to melt films. Consequently, the vapour which leaves the column and passes
and the corresponding temperature (melting-point) is immediately to the condenser is far richer in the more volatile constituent than
read. A pure solid will melt completely over a very narrow tempera- the original mixture.
ture range (less than 0.5°C). Impurity depresses the melting-point and For example, a mixture of equal volumes of 'methylated spirit* and
usually causes gradual softening instead of sharp liquefaction. To water will not burn in air. If it is distilled as in Fig. 70, and few cm 3
melt sharply at its recognised melting-point is good evidence of purity of the early distillate are put into an evaporating dish, the liquid will
for a known solid. burn readily on the application of a light. That is, the proportion of
alcohol is significantly increased. An efficient industrial still can
Fractional distillation deliver alcohol of about 96% concentration from a very dilute alcohol
If two liquids have reasonably different boiling-points, e.g., water wash produced by fermentation, but this mixture has a lower boiling-
100°C, ethanol (alcohol) 78°C at standard pressure, they can be point than any other water-alcohol mixture and distillation cannot
separated (though not always completely) by fractional distillation. purify it further.
Various forms of fractionating column can be used (Fig. 70). Their An column (as used, e.g., in distillation of
industrial fractionating
general purpose is to provide surfaces, e.g., flat discs, on which crude petroleum) will be cylindrical, made of steel and up to, per-
haps, 60-70 m
high. Hot vapour ascends through the middle of the
column. Trays at regular intervals round the walls collect layers of
Thermometer condensed liquid through which ascending vapour is forced to pass
by baffles. The column delivers fractions of distillate from various
points, with decreasing boiling-points higher up the column. See also
p. 324.

fractionating Determination of water of crystallisation

column
Barium chloride BaCI 2 .xH 2 0, provide a suitable case. A
crystals,
clean dry crucible weighed with lid. Two or three grams of barium
is

chloride crystals are added and the whole is weighed. The crucible,
with lid, is then heated on a pipe-clay triangle on a tripod, gently
at first and later strongly, to drive off water of crystallisation. The
whole is allowed to cool in a desiccator (to exclude moisture) and
weighed. It is then heated again, cooled as before and re-weighed.
This is repeated until a constant weight is reached which shows that
all water has been expelled.

Calculation
Wt. of crucible and lid a g
Wt. of crucible and lid and barium chloride crystals b g
Wt. of crucible and lid and barium chloride anhydrous c g
Wt. of water expelled (b — c) g
Wt. of barium chloride anhydrous (c — a) g
Fio. 70. xUfi (b - c)
Then
Fractional distillation. BaCl, (c - a)'
 NEW CERTIFICATE CHEMISTRY QUESTIONS 221
220 A
(b) Define the term solubility. What are the effects of temperature
and, inserting molecular weights,
and pressure on the solubility of (a) gases; (b) solids, in water?
_ {b-c) {b - c) Give the requisite practical details for constructing a solubility
x_
18s 208
and x curve of a salt, e.g., nitre. State two of the uses of a solubility
208 "(T^) ~(F=7) 1z curve. (B.)
1 1. A colourless liquid (X) is either pure water, or water containing some
dissolved solid. Describe carefully how to discover which it is by obser-
vations of the temperature at which it (a) boils; (6) freezes. Sketch the
QUESTIONS apparatus you would use in each case. Assume that a supply of pure water
is provided. (N.U.J.B.)
1. Explain the difference between (a) temporary, and (b) permanent 12. What do you observe when carbon dioxide is passed for a long time
hardness in water. Give the names of one substance causing temporary through lime-water? Give equations representing the reactions which take
and of two substances causing permanent hardness in water. Explain how place.
permanent hardness may be removed, giving equations for the chemical What happens when the final solution obtained is (a) treated with soap
changes involved. How would you test for the presence of a chloride in solution; (b) boiled; (c) treated with a solution of sodium carbonate.
tap-water? (N.U.J.B.) Describe the 'permutit' process for softening water and state how the
2. What are solubility curves? Of what use are they? What experiments permutit is restored (or revivified). (C.W.B.)
would you make in order to construct a solubility curve for potassium
chlorate? (O. and C.)
3. What are the substances which cause (a) temporary; (6) permanent
'hardness' in water?
Explain the effect of adding the following substances to 'hard' water:
(a)soap; (b) lime-water; (c) washing soda.
What is the 'fur' deposited in the kettle? Briefly explain how stalactites
and stalagmites are formed in caves. (B.)
4. What are the conditions, and what are the products, for the reaction
of the following substances with water or steam: (a) iron; (6) calcium;
(c) charcoal; (a") chlorine; (e) calcium carbide? (D.)

5. Imagine that you wish to prove experimentally to someone that 18

g of water contain 2 g of hydrogen and 16 g of oxygen. Give a labelled
sketch of the apparatus you would use; indicate the two chief precautions
you would adopt to ensure an accurate result; show how you would use
the data you obtain to prove the above statement. (N.U.J.B.)
6. Ordinary tap-water always contains some air in solution. Describe in
detailhow you would collect a quantity of this air from tap-water. How
could you find the proportion by volume of oxygen in such air? Explain
why the composition of this dissolved air will be different from that of
ordinary air. (N.UJ.B.)
7. State and explain what happens when carbon dioxide gas is passed for
a long time through lime-water. State and explain what happens when soap
solution is shaken with the final product (a) before it has been boiled-
(b) after it has been boiled. (N.U.J.B.)
8. What is meant by the terms 'saturated solution' and 'super-saturated
solution'? Describe exactly how you would proceed to determine the
solubility of potassium nitrate in water at 15°C. (N.U.J.B.)
9. What experiments would you make to find out whether (a) a given
sample of water hard or soft; (6) a gas-jar contains nitrous oxide or a
is
mixture of nitrogen and oxygen; (c) a given solid is sodium sulphide or
sodium sulphate? (O. and C.)
10. Choose either (a) or (b), but not both:
(a) Write an essay on 'combustion', giving a brief historical intro-
duction.
 ACIDS 223

Action on litmus. Most acids turn blue litmus to red. Some of the
weaker acids, however, for example carbonic acid, are so feebly

acidic that they can only turn the litmus to claret colour.
Corrosive action. The man in the street connects the term acid
Chapter 16 with the idea of a corrosive, 'burning' liquid. This is
because two of

the commonest —
acids sulphuric acid (oil of vitriol) and nitric acid
(aqua fortis)— are actually corrosive liquids. Acids are not, however,
generally corrosive and most of them are solids.
Acids, Bases and Salts Action with metals. Metals which are much more electropositive
than hydrogen (p. 134), react with dilute hydrochloric or
dilute

sulphuric acid (or both) to liberate hydrogen. The metals, e.g., Zn,
which are taken
ACIDS Mg, Al (with HCI only) and Fe, supply electrons
up by H+ ions of the acid, as:
ACIDS have a variety of properties (as stated but all theselater), Zn -»- Zn 2+ + 2e~
properties are derived from a single type of behaviour. This be- 2H + + 2«r-»-H 2
haviour is the production of the hydrogen ion, + , by acids when H A metal such as lead, which is only slightly more electropositive than
dissolved in water. Consequently, an acid can be defined in the
hydrogen, reacts with neither of these dilute acids, but will react in a
following way
similar way with hot, concentrated hydrochloric acid.
Definition.An acid is a compound which, when dissolved in water, Nitric acid is too strongly oxidising to allow the liberation of
produces hydrogen ions, II as the only positive ion.
hydrogen. Oxides of nitrogen are obtained. For a further account of
,

Examples are this, see p. 437.

Action with carbonates. Almost all acids (only the very weakest
Hydrochloric acid 1
HC1^ H + Cl- +

Sulphuric acid ^ 2H+ + S0 «-

H,S0 4 are exceptions) liberate carbon dioxide from a carbonate. The carbon-

Nitric acid HNO ^ H + + N0 -

4
ate supplies the ion, C0 3*-, which, with H
+ from the acid, gives the
s 3
reaction
The simple hydrogen ion (proton) is hydrated by water to form the 2H + + CO *--> H.O + CO,
s
hydroxonium ion, H 3 + but this complication is often ignored in
Action with bases and alkalis. This is very important but must be
,

the elementary consideration of acidity.

postponed (to p. 224) till the nature of bases and alkalis has been
H+ + H,0 ^ H„0 + considered.
If, as in the above three dilute acids, the ionisation is almost complete,
the acid said to be a strong acid. If the ionisation
Methods of preparation of acids
is is only slight, the
acid is said to be weak. For example, bench about
acetic acid is (1) By the reaction between an acid anhydride (the acidic oxide of
0.4% ionised, that is, only four out of every thousand molecules of a non-metal) and water.
the acid pass into the ionised state. Examples of this method are the preparation of sulphurous acid
and metaphosphoric acid by the action of sulphur dioxide and
CH 3COOH ^ H+ -f- CH 8COO"
Per thousand mol.
phosphorus pentoxide with cold water.
996 4 4
SO s + H tO ^H 2 S0 3 ; P 4 O 10 + 2H O -»- 4HP0 8
a

Some properties of acids

(2) By displacing a weaker or more volatile acid from its salt by a
Taste. Most
dilute acids have a sour taste. This is true of the three stronger or less volatile acid.
common mineral acids, sulphuric, hydrochloric and nitric, and of For example: (a) displacement of the more volatile hydrogen
many others. The sour taste of many unripe fruits, lemons and sour chloride from metallic chloride by the less volatile concentrated
milk is caused by the acids in them. sulphuric acid.
1
For HCI in toluene, sec p. 240. NaCl + H 2 SQ 4
-»- NaHSO« + HCI
222
224 A NEW CERTIFICATE CHEMISTRY BASES AND ALKALIS 225
(b) displacement of the weaker boric acid from borax by sulphuric
hydroxides. By reacting with an acid, i.e., with H+ , they produce
acid.
molecules of water.
Na,B 4 7 +H s SO< + 5H O t Na,SO« + 4H 8 B0 3 H + + OH- ^ H,0
(borax) (boric acid)
(3) By
precipitating an insoluble sulphide from a metallic salt by At the same time, the metallic ion from the oxide and the negative
hydrogen sulphide. ion from the acid remain, and together constitute a salt. Examples
of this are:
Pb(Ca H,O t) t + H 1 S- PbS + 2C a H«0,
(lead acetate) (acetic acid) Na+OH- + H+Cl--*- Na'Cl- + H 2
Ca 5+ (OH-) 2 + 2(H+N0 3 -)-v Ca st (NO a -) 2 + 2H,0
From these considerations, the following definitions can be derived:
BASES AND ALKALIS
Definition. A basic oxide (or hydroxide) is a metallic oxide (or hydrox-
A little earlier, an acid was characterised as a producer of H + in ide) which contains ions,
2- (or OH"), and will react with an acid
O
aqueous solution. To correspond with this, a base may be defined in to form a salt and water only.
the following way: It is important to realise the importance of the word only in these
Definition. A base is a substance which can combine with hydrogen definitions. If was omitted, certain compounds, which are quite
it
ion,H+. different from basic metallic oxides and hydroxides, would be in-
A number of bases are mentioned below and their combination cluded under the definition of base. Thus, lead(IV) oxide reacts with
with H + is shown. The reactions are reversible. If, as the equations hydrochloric acid to produce lead(II) chloride (a salt) and water,
are written below, the equilibrium lies strongly to the left, i.e., few but the word only excludes it from the class of bases because chlorine
molecules arc formed, the base is said to be weak; if the equilibrium is also produced.
lies strongly to the right, few ions remain, the base said to be
strong.
i.e., is
PbO a + 4HCI -> PbCl, + 2H 2 + Cl»
Compare this with the equations above. Lead(IV) oxide is clearly
Strength
Base Base Acid of Base
not a base.
The reactions between basic oxides, or hydroxides, and acids are
Chloride ion CI" + H+ HC1 very weak
Nitrate ion NO - +H HN0 3 very important and are called neutralisations. Since the metallic ions
a
l
very weak
Sulphate ion SCV" + 2H + H 2 S0 4 and anions from the acid do not change (see the two equations above),
very weak
CH3COO- + H+ the essential reaction of a neutralisation is always the formation of
Acetate ion CH3COOH strong
OH-+ H* unionised molecules of water from hydroxide and hydrogen ions
Hydroxyl ion H8 very strong
(or hydroxonium ions).
obvious that a base exists corresponding to each acid. The
It is
corresponding pairs can be called conjugates and, if the acid is weak,
H + OH-^H gO
+ or H sO + + OH~ ^ 2H 2
the base is strong, and vice versa. For practical purposes, these reactions are complete from left to
At the chemical level for which this book is intended, the most right.This leads to the following definition.
important of all the bases is the hydroxyl ion, OH". It is a very Definition. Neutralisation is the formation of molecules of water from
strong base indeed, and when it combines with hydrogen ion, the hydroxide ions,
-
OH
and hydroxonium ions,
, 3 H
'. A salt is formed

water formed is almost completely unionised, i.e., from this point of at the same time.
view, water acts as a very weak acid. Metallic oxides and hydroxides The following are examples of neutralisations. Notice that the
are usually electrovalent compounds, containing the ion, 2 ~ metallic ions and the negative ions from the acids remain to produce
(oxides), or OH-
(hydroxides), in addition to the metallic ion. The the salts.
ion, O*-, can enter the equilibrium: O*-
g 20H~ with +HO^ Acid Basic hydroxide Salt Water
water. Consequently, metallic oxides and hydroxides of this kind
can produce the base, OH~, and are known as basic oxides or H.O+C1- + K+OH- — K + C1- + 2H O a
H3 + N0 3 - + Na + OH- —> Na + N0 - + 2H,0 3
226 A NEW CERTIFICATE CHEMISTRY SALTS 227

SinceboththesereactionsreducetoH sO + +
OH-—*-2H 8 0,theenergy Expressed in molecular form, two examples of this are:
change accompanying both should be the same. This is, in fact, so. NaOH + NH 4 CI -> NaCl + H aO + NH 3
If aqueous acidic solutions are made up containing one mole of (ammonia)
HCI, HNO s and $H 2 S0 4 in 1 dm 3 and alkaline solutions containing (NH 4)2S0 4 ->- CaS0 4 + 2H aO + 2NH 3
one mole of NaOH and KOH in 1 dm 3 (i.e., strong acids and alkalis),
Ca(OH) 2 +
any neutralisation between these solutions liberates the same amount Salts
of heat energy, viz., 57.3 kJ (13.7 kcal). This was surprising in an on 225, applied to a product
We have encountered the term salt p.
earlier 'molecular' context because all the compounds appeared to
of the process of neutralisation. A
salt was seen to consist, from this
have separate identities. Ionic ideas, however, require all strong view, of an aggregation of metallic ions (positively charged)
point of
acids and alkalis (and the salts they produce) to be completely ionised
and acidic ions (negatively charged). Consequently, a salt is derived
from the acid to which it corresponds by replacing the H of the
in dilute solution. Consequently, the only significant change between acid '

them in neutralisation is:

equivalent number of metallic ions. Examples are:
by an
H,0+ + OH - -»- 2H 2 0; A// = -57.3 kJ
Acid Salt

Alkalis H+Cl- Na + Cl _ sodium chloride

- Cu 24 S0 42 - copper sulphate
A definition of basic hydroxide has been given above. If such a (H*),S0 42
_
hydroxide is soluble to a considerable extent in water, it is known as H + NO - K + N0 3 potassium nitrate
an This gives the definition:
alkali. (H+) 2 W" a
Ca z+ CO a2 - calcium carbonate

An alkali is a basic hydroxide which is soluble in water.

Definition.
Notice that the salt is electrically neutral by a balancing of the
Only a few alkalis are known. The common ones are sodium
oppositely charged ions.
hydroxide (caustic soda), NaOH, potassium hydroxide (caustic
potash), KOH, calcium hydroxide (slaked lime), Ca(OH) 2 and ,
Normal and acid salts
ammonia solution. This property of solubility in water is the only
When an acid can produce more than one hydrogen ion per mole-
difference between the select little group of alkalis and the basic
cule, possible for the replacement of H+ by metallic ion to occur
it is
hydroxides generally, but a very important difference. It puts the
it is
+ ions of sulphuric acid, (H + ) 4 S0 4 2 -,
alkalis at our service in hundreds of reactions in solution and for a in stages. Thus, one of the H
+
great many purposes for which the insoluble basic hydroxides are
may be replaced by the ion, Na , to give sodium hydrogen sulphate,
Na + HS0 4 -, after which a second, similar replacement may yield
quite useless. It must be clearly realised that the alkalis have all the +
sodium sulphate, (Na ) 2 S0 4 -. Salts like Na HS0 4 partake of
+ 2 "
properties of basic metallic hydroxides in general, but possess also
the nature of a salt because they contain a metallic ion and a negative
the property of dissolving to a substantial extent in water. Slaked
an acid because
lime is the least soluble of the common alkalis (about 0.15 g in 100 g ion derived from an acid ; they partake of the nature of
the negative ion is capable of further
ionisation to yield H+, as:
of water at room temperature).
HSO t
_ ^
H+ S0 42_ Having this dual nature, they+ are called
+ .

Properties of alkalis acid salts. Salts like sodium sulphate, in which all the of the acid H
has been replaced by metallic ion, are known as normal salts.
In addition to the very important property of neutralising acids,
Definition. salt is a compound consisting of positive metallic ions
A
already dealt with above, alkalis also have a bitter taste and turn red
and negative ions derived from an acid; if the negative ions are capable
litmus blue. Further, the two caustic alkalis, and KOH, haveNaOH H* the salt isan acid salt, but if not, the
a powerful corrosive action on the skin and should be treated with of further ionisation to yield

care. Just as a non-volatile acid displaces a volatile acid

salt is a normal salt.
from its
salts, a non-volatile alkali displaces the volatile ammonia from Examples:
ammonium salts. If an ammonium salt is warmed with an alkali (in Acid Acid salt Normal salt

the presence of water), ammonia gas is liberated. The essential reac- + ),S0 «- Na+HS0 4 - (Na + )e S0 4*-
(H 4
tion is: (sodium sulphate)
(sodium hydrogen
NH 4
< +OH--*NH 3 + H 2 sulphate)
 :

228 A NEW CERTIFICATE CHEMISTRY METHODS OF PREPARING SALTS 229

Acid Acid salt Normal salt Practical details of the more important methods of making salts

(H+) a CO,»- Na^HCOr (Na+) t CO,«- are given in the following pages.
(sodium hydrogen (sodium
carbonate) carbonate) METHODS OF PREPARING SALTS
2-
(H +) SS Na+HS" (Na + ),S 2-
Rules of solubility of salts in water
(sodium hydrogen (sodium sulphide)
sulphide)
SOLUBLE INSOLUBLE
A method of preparing normal and acid sodium salt of
the
sulphuric acid is given on p. 412, of the normal and acid sulphides
1. All common salts of sodium,
of sodium on p. 400 and of sodium carbonate and hydrogen car-
potassium and ammonium.
bonate on p. 312.
2. All common nitrates of metals.
3. All common chlorides except silver chloride, mercurous chlor-
Basicity of an acid ide and lead chloride.
We have seen that it is characteristic of an acid to yield H* in 4. All common sulphates except barium sulphate and lead sul-
aqueous solution. The number of H+ ions produced per molecule of phate. (Calcium sulphate spar-
the acid is called its basicity. ingly soluble.)
Definition. The basicity of an acid is the number of hydrogen ions, 5. All common carbonates except
H*, which can be produced by one molecule of those of sodium, potassium
the acid.
and ammonium (see Rule 1).
Acid Basicity

HC1 ^H +
+C1- Monobasic
Several general methods are available for preparing salts. The
H 2 S0 4 ^ 2H + + S0 4 «- Dibasic
method chosen for preparing any particular salt depends largely on
H 3 P0 4 ^ 3H+ + P0 4 3 ~ Tribasic
necessary, therefore, for
whether it is soluble in water or not. It is

Notice that the basicity of an acid is not necessarily the number of
hydrogen atoms contained in one molecule of it. For example, acetic
acid, CgH 4 2 , though containing four hydrogen atoms per molecule,
is only niowobasic. Three of the four hydrogen atoms are so com-
bined as to be incapable of ionising.
you to become quite familiar with the simple rules of solubility
above. Knowing the solubility of the salt, you will then be able to
decide at once what type of method to use.
Soluble salts are usually prepared by methods which involve
crystallisation. Insoluble salts are usually prepared by methods which

QH 4 8 c* H+ + C.HA- involve precipitation.

Preparation of soluble salts by the action of an acid upon a metal

Basic salts
This is usually carried out using a dilute acid and a metal. The salt
Basic oxides or hydroxides (p. 225) contain the ions, O 2- or OH - , formed then passes water of the dilute acid and
into solution in the
respectively. Salts in which these ions are retained, together with can be obtained, with the necessary precautions to give purity, by
metallic ions and the negative ions of acids, are known as basic salts. crystallisation. This method is suitable for preparing soluble salts.

For example Preparation of a sample of crystalline zinc sulphate (white vitriol)

Basic hydroxide Basic salt Normal

from metallic zinc. Half-fill a beaker with bench dilute sulphuric
salt
acid and add granulated zinc. Effervescence occurs; if it is slow, add
Zn^(OH-), Zn* + OH-Cl- Zn 2+ (Cl-) t a little copper sulphate to quicken the action and warm gently. The
Mg2+ (OH-)„ Mg2+ OH-Cl- Mga+ (Cl-) 2 gas is hydrogen (test: explosion on applying a lighted taper). If the
The basic salts quoted in the table are known as basic zinc (or
action ceases because of the disappearance of zinc, add more zinc to
magnesium) chloride. a well-known basic salt and is the
White lead is
The reason
make sure that the acid is not left in considerable excess.
basic carbonate of lead, 3Pb 2T 20H-2C0 3 8 -. Notice that the ionic and any excess
for this is that later we shall evaporate the solution
charges balance so that the salt as a whole is electrically neutral.
230 A NEW CERTIFICATE CHEMISTRY METHODS OF PREPARING SALTS 231

acid would then tend to become concentrated. When the effervescence Occasionally this method is applied using a metal and a concen-
slows down and thereplenty of zinc left, filter to remove in-
is still The only case of this you will encounter, though it is an
trated acid.
soluble impurities such as excess zinc and particles of carbon which important one, is
were an impurity in it. Preparation of a sample of blue copper sulphate)
vitriol (crystalline
The colourless solution will contain zinc sulphate together with a from metallic copper. Note especially that preparation
this cannot be
little sulphuric acid. There will probably be too much water present carried out like the three above, because dilute sulphuric acid will not
to allow the crystals to separate, so we must remove some of it. Place act upon copper.
the solution in an evaporating dish and heat. At intervals, pour a Into a beaker put some concentrated sulphuric acid and coppet
of the solution into a test-tube and cool it under the tap, shaking
little turnings (care!). Put the beaker on a tripod and gauze in the fume-
well. After evaporating for a time, you will see small crystals in one cupboard and warm gently. After a time effervescence will begin, the
of the cooled samples. This shows that the solution will give crystals gas evolved being sulphur dioxide, which must not be allowed to
when cool, for the small sample is typical of the whole. Pour the escape into the laboratory as it is injurious. The action will probably
solution into a beaker and allow it to cool and crystallise. In this become vigorous, and the flame should then be removed. After
case the crystals will be colourless needles. effervescence has ceased there will be left a dark brown mass which
Filter off the crystals, wash them two or three times with a small may contain the following substances:
quantity of cold distilled water and place them on a porous plate or 1. Solid copper sulphate as a precipitate. (This is copper(II)
between filter-papers to dry. The washing with distilled water is to sulphate.)
remove the surface solution from the crystals and replace it with pure 2. Solid dark brown copper(I) sulphide, formed in small amount,
water which, as it dries off, will not deposit impurities as would the by a side reaction.
solution. The porous plate or filter-papers are used to absorb water 3. Excess copper.
from the surfaces of the crystals. To purify still further, dissolve the 4. Excess concentrated sulphuric acid.
crystals in a little very hot water and repeat the crystallisation process.
Our problem is to prepare from this mixture a sample of pure blue
The impurities will then be carried off dissolved in the filtrate and a
vitriol. Wecannot work in the presence of a large amount of con-
smaller quantity of purer crystals will be left.
centrated sulphuric acid, so the first step must be to pour off as much
Zn + H 2 S0 4 -> ZnSO« + H2 liquid as possible. The liquid is simply a waste product. We are now
Zn + 2H + -v Zn*+ + H 2 )
(or
left with a solid containing copper sulphate with impurities 2 and 3,
ZnS0 4 + 7H gO ->- ZnS0 4 .7H 2 as given above. They are both insoluble in water, so, to remove them,
Other salts may be similarly prepared, for example, iron(II) sul- add a considerable quantity of water and heat gently to boiling.
phate and magnesium sulphate. Filter, leaving the two impurities, copper and copper(I) sulphide, on
Preparation of iron(II) sulphate crystals (green vitriol). Use iron the filter-paper, and obtaining, as filtrate, blue copper sulphate
filings or wire and excess dilute sulphuric acid. The solution and solution. From this, crystals can be obtained as previously described.
crystals are green. Cu + 2H 2 S0 4 ->- CuS0 4 + 2*1*0 + S0 2
Fe + H 2 S0 -»-FcS0 -f-H
4 4 2 CuS0 4 + 5H 20-> CuS0 4 .5H,0
(or Fe + 2H+ -* Fe*+ + H 2)
This process of heating copper with concentrated sulphuric acid is
FeS0 + 7H sO-> FeS0 4 .7H
4 2
the best laboratory method of making sulphur dioxide, and copper
(iron(II) sulphate crystals)
sulphate can be prepared from the residue left in the flask after carry-
Preparation of magnesium sulphate crystals (Epsom salt). Use
ing out this preparation (p. 403).
magnesium rod and dilute sulphuric acid. The solution and the
Nitrates of certain metals can be prepared by acting upon the metals
crystals are colourless. with dilute or concentrated nitric acid and crystallising as described
Mg + H 2 S0 4 -»- MgS0 4 + H 2 (p. 230). The nitrates of common heavy metals, except lead nitrate,
Mg + 2H+ -»- Mg2+ + H 2 )
(or are, however, very soluble in water and deliquescent. This makes it
MgS0 4 + 7H 2 -> MgS0 4 .7H 2 a matter of greater difficulty to prepare their crystals.
+ 8HN0 8 - 3Pb(N0
(magnesium sulphate
crystals) 3Pb 3) 2 -f 4H 2 + 2NO
232 A NEW CERTIFICATE CHEMISTRY METHODS OF PREPARING SALTS 233

3Cu + 8HNO a -> 3Cu(NO a) 8 + 4H 2 + 2N0 The sodium nitrate, like the nitric acid above, would be removed in
copper coppcr(II) nitrate solution.
Chlorides of heavy metals are generally prepared in the anhydrous Other insoluble salts which can be prepared by double decom-
state by heating the metal in a current of dry chlorine or hydrogen position are:
chloride (see p. 372). Barium sulphate BaCl 2 4- H S0 2 4
->- BaS0 4 + 2HC1
The reason for this is many of them crystallise with water of
that barium
chloride
crystallisation, and, if an attempt is made to drive off this water by
heating, they hydrolyse to basic salts (see p. 228). ionically: Ba*+(aq) + S0 *"(aq) -»- BaS0 4 (c)
4

Thus: ZnCl 2 .H 2 -^ Zn(OH)Cl 4- HC1 Lead chloride 1

Pb(N0 + 2NaCl -> PbCl 2 + 2NaNO
3) 2 s

ionically: Pb s+ (aq) + 2Cl~(aq) -» PbC! 2(c)

Preparation of salts by double decomposition Calcium carbonate CaCl 2 4- Na 2CO s ->- CaC0 3 4 2NaCl
we usually begin with two calcium
In a double decomposition reaction,
chloride
soluble compounds and use them to prepare one soluble and one in-
soluble compound (p. 160). Of these, the one which is wanted is ionically: Ca2+ (aq) 4- C0 3 ~(aq) -*- CaCO s(c)
usually the insoluble compound for it can be easily separated by The carbonates of other heavy metals can be prepared like calcium
filtering.That is, insoluble salts are prepared by double decom- carbonate but, in some cases, the method gives a basic carbonate.
This does not matter much, however, because the method is
position. For a more complete discussion of double decomposition chiefly

see p. 160. In what follows, all lead salts are lead(II). used as an intermediate stage in preparing the oxide of a metal from
To prepare a sample of lead sulphate. Here we must begin with a one of its soluble salts (p. 243), and in this case it does not matter
soluble lead salt to provide the lead ions, and a soluble sulphate to whether a true or a basic carbonate is precipitated.
provide the sulphate ions of the lead sulphate. Suitable compounds In the cases of zinc carbonate, copper carbonate and lead car-
will be lead nitrate and dilute sulphuric acid (a soluble sulphate). bonate, a purer product is obtained if sodium hydrogen carbonate is
One-third fill a beaker with lead nitrate solution. Heat it and add used instead of sodium carbonate.
dilute sulphuric acid, stirring the mixture. There will be an immediate
white precipitate of lead sulphate. Heat to boiling, 1 then filter. The Preparation of salts by neutralisation
lead sulphate is left on the filter-paper and the colourless filtrate con- Neutralisation is an action between a base and an acid to produce a
tains dilute nitric acid, the other product of the double decomposition saltand water only (p. 225). The actual method of application of this
reaction. Wash the precipitate on the filter-paper several times with process depends on whether the base in question is soluble in water,
hot distilled water to remove soluble impurities. To be sure that the that is, is an alkali (p. 226) or not.
process is complete, test the washings for sulphate (p. 416) and con-
tinue till the test gives a negative result. Allow the precipitate to dry Preparation of a salt from an alkali (a soluble base)
on the filter-paper or on a porous plate. It will become a white and ammonium can be prepared
Salts of sodium, potassium
powder. method from caustic soda (sodium hydroxide),
by this
Caustic potash (potassium hydroxide) and ammonia (ammo-
Pb(N0 3) 2 + H S0 2 4
-»- PbSO« + 2HN0 3 nium hydroxide) respectively, using the appropriate acid.
A solution of any soluble sulphate could have been used for this
preparation; for example: To prepare sodium sulphate from caustic soda. Into a conical flask,
put 50 cm8 of bench caustic soda solution and add to it enough
Pb(N0 3) 2 4 Na S0 -> PbS0 + 2NaN0
2 4 4 3
litmus solution to give a pale blue liquid. From a burette, add dilute
lead sodium lead sodium
nitrate sulphate sulphate nitrate sulphuric acid until the solution is purple in colour; that is, it con-
ionically: Pb2+ (aq) 4- S0 4 2 "(aq) -> PbS0 4 (c) tains no excess of either acid (which would make the litmus red), or
1
The chief reason for this is that a boiling solution filters more rapidly than a 1
Lead chloride must be washed with cold distilled water, as it is appreciably
cold one. soluble in hot water.
234 A NEW CERTIFICATE CHEMISTRY METHODS OF PREPARING SALTS 235

base
alkali (which would make the litmus blue). The litmus is here the preparation of a soluble salt from an insoluble
indicator (p. 239). The solution now contains sodium sulphate solu- in water, is not an alkali, so
In thiscase the base, being insoluble
tion together with litmus. To remove the litmus, add a little animal
the method given above cannot be applied. In what follows, all
charcoal on the end of a spatula, boil the mixture, and filter. The are copper(II) and lead(II) compounds.
copper and lead compounds
animal charcoal will be left on the filter-paper together with the prepare copper sulphate crystals from the insoluble base, copper
To
litmus which it has absorbed, and a colourless solution of sodium sulphuric acid in a beaker and add to it, a
oxide Heat some dilute
left as filtrate. From this, crystals can be obtained as
sulphate will be
little at a time,
some black copper oxide. Stir gently. A blue solution
described above for zinc sulphate (p. 230). will be formed.
of copper sulphate
2NaOH + H 2 S0 4 -»- Na S0 4 + 2H 2 2 CuO +H
S0 4 ->- CuS0 4
2
+ H,0
Na 2 S0 4 + 10H a O-> Na 2 SO 4 .10H 2 O see prepara-
It isadvisable not to leave an excess of acid (for reason
from zinc), so continue the addition of the
To obtain sodium chloride or nitrate, use caustic soda solution with tion of zinc sulphate
permanent black precipitate of this material is
the appropriate acid. copper oxide until a
that no more acid is available to act with it. Filter off
left showing
NaOH + HC1 ->• NaCl +H 2
the'precipitate,leaving a clear blue filtrate, copper sulphate solution.
sodium dilute sodium
hydroxide hydro- chloride From it, obtain crystals as described for zinc sulphate.
chloric acid
CuSO« + 5H 2 -* CuS0 4 .5H 2
NaOH + HNO s - NaN0 3 + H 2 using either the
Many salts of metals can be similarly prepared,
diluic sodium
hydroxide of the metal with the appropriate acid; for
nitric acid nitrate oxide or the
To obtain the common potassium salts, use caustic potash solution example,
with the appropriate acid. Zinc sulphate ZnO + H 2 S0 4 -> ZnS0 4 +H 2

zinc
KOH + HCI -»- K.C1 +H 2 oxide
potassium potassium
hydroxide chloride Zn(OH) 2 H S0 -*ZnS0 + 2H
2 4 4 B
zinc
2KOH + H 2 S0 4 -»- K 2 SO« + 2H tO hydroxide
potassium
sulphate Lead nitrate PbO + 2HN0 3
-
Pb(N0 3) 2 +H 2

lead
KOH + HN0 3
->- KNO a + H O t oxide
potassium
nitrate Pb(OH), + 2HN0 3 Pb(N0 3) 2 -I- 2H 2
lead
Ammonium salts can be similarly prepared from ammonia. hydroxide
NH 4 OH + HCI -*• NH 4 C1 + H aO carbonate of a
ammomum Preparation of salts by the action of an acid on the
chloride
metal
2NH 4 OH + H 2 S0 4 (NH 4) 2 S0 4 + 2H 2 The carbonate of any metal will react with the mineral
ammonium and
sulphate acids to give the corresponding salt of the metal, water
carbon dioxide.
NH OH + HN0
4 3
-
NH NO a + H O
4 t
ammonium For example : ZnC0 3 + H 2 S0 4 -> ZnSO« + H»0 + CO s
nitrate zinc z'nc
carbonate sulphate
The above equations indicate the substances to be used (all in
solution) in the preparation of the salt by the method described for CaCO a + 2HC1 ->- CaCl, +H 2 + CO,
calcium calcium
sodium sulphate. carbonate chloride
236 A NEW CERTIFICATE CHEMISTRY pH scale 237

PbC0 3 + 2HN0 3 Pb(NO s), + H sO +

-
CO.. Similarly, to convert chalk to calcium sulphate, do not attempt the
conversion by using dilute sulphuric acid directly with the chalk. First
lead(II) Icad(ll) nitrate
carbonate
dissolve the chalk in dilute nitric acid.
The only limitation to this rule is that the action is unsatisfactory
and incomplete if the carbonate is insoluble in water and, by its
CaC0 3 + 2HN0 3 ->- Ca(N0 3 ) 2 + H,0 + CO,
action on the acid, produces a salt which is also insoluble. In this Then filter, and, to the hot filtrate, add a concentrated solution of
case, the salt which is formed precipitates on the unchanged carbon- sodium sulphate.
ate and stops the action. If, for example, dilute sulphuric acid is Ca(NO s ), + Na.,S0 4 -> CaS0 4 + 2NaNO a
added to marble, there is rapid effervescence for a few seconds, but calcium sulphate (or lead sulphate above) wash
Filter the precipitated
the action quickly stops.
it with hot distilled water and allow it to dry.
CaCOj + H,S0 4 -»• CaS0 4 + H,0 + CO,
Preparation of salts by direct combination of two elements
The very slightly soluble calcium sulphate has precipitated on the
marble, stopping the action. With this limitation, this method is of Certain binary salts can be prepared by direct combination of their
two elements; for example,
general application. Lead compounds below are lead(II) compounds.
Preparation of lead nitrate crystals from lead carbonate. Half-fill a 2Fe + 3Cl,->- 2FeCl 3 (see p. 362)

beaker with dilute nitric acid, warm it gently on a tripod and gauze iron(lH) chloride

and add lead carbonate at intervals. There will be effervescence with Fe + S -*- FeS (see p. 7)
iron(ll) sulphide
evolution of carbon dioxide. (Test: lime-water turned milky.) Con-
tinue the addition of the carbonate until a slight permanent precipi- pH scale. This scale is a convenient means of expressing acidity and
tate shows that no acid is left, then remove insoluble materials.
filter to alkalinity in aqueous The term, pH, denotes hydrogen ion
liquids.
The colourless solution contains lead nitrate, and crystals can be index, the p being derived from European use of terms such as punkt
obtained from it as described for zinc sulphate (p. 230). or point for the English index. The pH scale can be used with the mini-
PbC0 8 + 2HNO a ->- Pb(N0 3 ), + H,0 + CO, mum information contained in the next paragraph but students are
advised to read the later material which explains more adequately the
Note. When an insoluble salt has to be prepared from a
source of the scale and the significance of the numbers in it.
compound which is also insoluble in water, it is not ad-
The number 7 on the pH scale represents the condition of pure
visable to try to convert one into the other by a single pro-
water in relation to acidity and alkalinity, i.e., the condition of exact
cess.
neutrality. Numbers less than 7, i.e., pH 6, 5, 4, etc., indicate acidity

For example: To convert lead oxide, PbO (insoluble in water) increasing as the numbers decrease; numbers greater than 7, i.e., pH 8,
into lead sulphate (also insoluble in water), it is not advisable 9, 10, etc., indicate alkalinity increasing as the numbers increase.
to attempt the change by the action of dilute sulphuric acid on the
oxide. The reason is that the insoluble lead sulphate will precipi-
tate, as fast as it is formed, round the particles of oxide, and it
very difficult to make sure that all the oxide has reacted.
is
pH 1

«
2 3

increasing
acidity
4 5 6 7

t
Neutral
8 9 10

—— 11
;

increasing
alkalinity
12 13

In such cases, it is better to prepare first a soluble compound and pH values indicate in-
Notice particularly that, below 7, falling
then to precipitate the required insoluble salt by double decomposi-
creasing acidity; above 7, rising pH
values indicate increasing alkal-
tion. In the example above, it is better to prepare first a solution of inity. For the mathematical explanation of this, see later. In a colour-
lead nitrate by dissolving the oxide in dilute nitric acid.
less liquid, a reasonably accurate value of pH can be obtained by
PbO + 2HN0 3 -» Pb(N0 ), + H,0 3 adding a universal indicator(in quantity advised by the supplier) or by

spotting the liquid on to universal indicator paper. In both cases, a

Then, after filtering off any undissolved material, the required lead
sulphate can be precipitated by adding dilute sulphuric acid. colour will appear from which the pH of the liquid can be decided,
either by verbal description or from a series of sample tubes provided
Pb(NO s ), + H,S0 4 -» PbS0 4 + 2HNO, by the supplier for colour matching.
 238 A NEW CERTIFICATE CHEMISTRY pH SCALE 239

Explanations It would be possible to use a hydroxyl ion index, pOH, to indicate

such a usage can be avoided. This is because,
Ionic state of pure water. Hydrogen ion index, pH alkalinity but, in fact,

Pure water is very slightly ionised and in all cases,

is, therefore, a very weak
electrolyte. [H + ][OH-] = 10-" = Kv
pH + pOH = and pOH = 14 - pH
H aO^H + OH- + or 2H sO ^ H s O +
+ OH~ so that 14

This constant relation enables pH to record

alkalinity (as well as
(The first of these equations is still in common
use for simplicity
though it is known that the hydrogen ion (proton) is hydrated in acidity) as in the following case. 0.01 M
potassium hydroxide solution
contains 10" mole/dm of OH". This would give pOH
a 3 2 and =
aqueous solution to give the hydroxonium ion, sO .) From con-
+ H = - = That pH indicates alkalinity by
ductivity measurements, it is known that, in mole/dm s , the con- require pH 14 2 12. is,

centration of the two ions in water is lO -7 , so that their product is values higher than 7.
given by: pH
[H +][OH-] = 10-' x 10-' = 10-" = Kw (at 25°C)
Acidic below 7
where KK is called the ionic product of water. This ionic product is
7
Neutral
maintained constant in all circumstances in water at 25°C. When the
Alkaline above 7
concentrations of H+ and OH~ are equal, the liquid is exactly
neutral and both ion concentrations are 10~ 7 mole/dm3 If the liquid .

is made acidic, H+ above 10~ 7 mole/dm 3

concentration is raised Universal indicator. A is a mixture of indi-
universal indicator
can indicate pH
.

Then, to maintain the value of K„, OH~ concentration must be cators, often sold ready-made which
as a solution,
reduced correspondingly below 10- 7 mole/dm 3 For example, in values, usually over a range of about 3-11, by successive changes of
.

0.01 M
strong monobasic acid, [H+] = 10-*, so that colour. A recognisable colour change takes place for every change of

x [OH-] = 10-" and one unit of pH and, over certain ranges, only half a unit.
10-°-
[OH"] = 10""
for pH by adding the universal indicator
A given solution is tested
If the liquid is made alkaline as, say,
0.001 sodium hydroxide M to it proportion stated by the supplier, usually two drops of
in the
solution,[OH-] = 10"3 so, to maintain the value of Ku [H,+] must
,
indicator solution lo 10 cm 3 of test solution, with shaking. The
decrease to 10 -u This gives the following situation:
colour which develops shows the pH of the solution either by recog-
.

nition from a verbal description given on the indicator label or

by
Aqueous liquid H ' cone. OH - cone.
matching to sealed sample tubes provided by the supplier for pH
3, 4, 5, etc., up method is suitable for colourless liquids
to 11. This
only (for obvious reasons). Knowledge of pH values is important
Neutral [10-1 [10- 7]
Acidic above [10- 7] below [10- 7] for many industries, e.g., for control of soil condition in
farming and
Alkaline below [10- 7] above [10- 7] horticulture, for control of water supplies and sewage disposal.

As a convenient means of expressing Anordinary single indicator usually requires a change of about 2
these situations, the hydrogen
ion index, pH, has been introduced. This index is derived in the fol-
units of pH to bring about its complete colour change. For example,
lowing way. litmus is fully red at pH 6, purple at pH 7 and fully blue at pH 8.
The three common indicators for acid-alkali titration are the fol-
-
If in an aqueous liquid, concentration of H+ is 10 " lowing.
mole/dm 3 , then, for that liquid, pH = x.
Acidic side '
Neutral Alkaline side
From this follows (above table) that neutrality is indicated by
it

pH = 7. Notice that pH is a logarithmic index from which the Methyl orange pink orange yellow
negative sign has been omitted. Consequently, the greater the num- Litmus red purple blue
erical value of pH the lower is the concentration of + and the less H Phenolphthalein colourless '
colourless '
pink
the acidity.
-2 pH units increase-
 240 A NEW CERTIFICATE CHEMISTRY QUESTIONS 241

Hydrogen chloride in toluene Describe one laboratory method of preparing specimens of each of
3
The CH the 'following: (a) copper
from copper(II) sulphate; (b) solid sodium
solvent, toluene,
4 B .CH 3 , hydrogen
readily dissolves
chloride in room conditions, but (in contrast to aqueous hydrogen hvdrogen sulphate from sodium hydroxide; (c) potassium chlorate from
potassium hydroxide; (d) anhydrous iron(III) chloride from iron. (B.)
chloride solution) the liquid is a non-conductor of electricity and has
4. Give four general methods of
preparing acids, illustrating each
negligible acidic behaviour, e.g., no reaction with metals (Zn, Mg, Fe)
method by two examples. . .

and only very slight reaction with carbonates. These differences are Describe experiments by which you could determine the basicity of
present because toluene is not a proton (H + ) acceptor and the dis- sulphuric acid. (L.)
solved hydrogen chloride remains overwhelmingly in the molecular Describe, giving experimental details, how you would prepare
5.
state as HCI; the solution is, therefore, electrically non-conducting crystalline specimens of (a) potassium nitrate starting from potassium
for lack of ions. hydroxide; (6) lead(II) nitrate starting from red lead ; (c) sodium hydrogen
sulphate starting from sodium hydroxide. (N.U.J.B.)
Water, however, is a proton acceptor and, in dilute aqueous solu-
Starting from metallic zinc, describe carefully how you
6.
would prepare
tion, hydrogen chloride can be taken as fully ionised. carbonate.
HCI + H aO - H 0+ + 8 Cl-
reasonably pure specimens of

crystallisation. Calculate the

(a) zinc sulphate; (&) zinc
The zinc sulphate crystals are found to contain 43.9% of water of
number of molecules of water in combination
These ions allow ready electrical conductance through the liquid
with one molecule of the anhydrous salt. (O.)
and the hydroxonium ion liberates hydrogen with the more electro-
7. Explain clearly what is meant by a 'normal' salt, an acid salt, and a
positive metals and carbon dioxide with carbonates.
peroxide, giving two examples of each.
Zn + 2H 30+ -»- Zn* + + 2H,0 + H, Describe experiments by which you could prove that red lead contains
lead and oxygen, but no other elements. (L.)
2H sO+ + CO,*--*- 3H,0 + CO, basicity of an acid.
8 Explain with examples what is meant by the
These reactions are not given in toluene for lack of a
+ If HO . 2 grams of oxalic acid which crystallises with two
molecules of water are
is formed
ammonia (gas) is passed into it, a solution of hydrogen chloride in heated with concentrated sulphuric acid. What volume of gas
at 13°C and 570 mm? If this gas were
allowed to stand over potash, what
toluene precipitates ammonium chloride (white solid).
volume of gas would remain at s.t.p. (L.)
NH 3 + HCl->-NH 4 +Cl- 9 How would you prepare (a) crystalline sodium carbonate
starting
metallic lead;
from sodium hydroxide; (6) lead(II) sulphate starting from
hydroxide solution starting from sodium carbonate? (N.U.J.B.)
(c) sodium
QUESTIONS and E, D
said to have pH
10 You are supplied with solutions A, B, C,
1, Describe fully, giving complete experimental details, how you would Classify these solutions as
values of (A) 2, (B) 7, (C) 7.5, (D) 13, (E) 6.5.
prepare the following. Consider in each case the solubility of the required alkaline. Describe
neutral, slightly or strongly acidic, slightly or strongly
compound and decide first which of the methods given in the last chapter a practical method by which you would verify one of the pH
figures
is the best for the given case. In some of them it is advisable to use two would be most likely to liberate hydrogen with
quoted. Which solution
steps (see Note, p. 236). magnesium powder? Which other solution would be most likely to liberate
(a) Copper(II) sulphate crystals starting from malachite, basic copper(II) hydrogen with aluminium powder? Write equations for both reactions.
carbonate, CuCO,.Cu(OH),.
(b) lron(ll) sulphate crystals starting from iron wire.
(c) Nitre (potassium nitrate).
(d) Calcium sulphate starting from marble (calcium carbonate).
(e) Sal-ammoniac (ammonium chloride).
(/)Lead(II) chloride starting from lead(II) carbonate.
(g) Zinc sulphate crystals starting from zinc oxide.
(h) Sodium chloride, common salt.

2. Describe fully, with complete experimental details, how you would

prepare (a) copper(II) sulphate crystals from a mixture of charcoal and
black copper oxide; (.b) zinc sulphate crystals from the commercial product,
'zinc dust', which contains zinc and zinc oxide; (c) a pure sample of
barium sulphate and zinc carbonate, normal or basic, from a mixture of
zinc oxide and barium carbonate.
 .

OXIDES 243

If strongly heated, it passes into a

form which is insoluble in both

acid and alkali.

Uses. The most important form of this oxide is bauxite, AlgO s .

2H gO, from which the metal isextracted, p. 477. It also occurs in an

Chapter 17 impure form as emery and is used as an abrasive.
Coloured by the presence of impurities, this oxide occurs as the
gems, ruby (iron and titanium), sapphire (chromium) and amethyst
(manganese).
Oxides common heavy
Summary of preparation of the normal oxides of some
metals from the metals or their soluble salts
Metal (Pb, Cu, Mg, Zn)
THE BASIC OXIDES
THESE oxides are the ones which correspond to the commonly dilute nitric acid
occurring salts.
nitrate of metal
K Oxides of these metals are in solution
Ca ^soluble in water forming
Oxides of these metals not
Na alkalis
^reduced to metal by
Mg hydrogen solid nitrate add NaOH solution1 add Na 2 C0 3 solution 1
A) Oxides of these metals can <
•

T
Zn be made from the metal he at hydroxide of metal carbonate of metal
Fe by the action of nitric stro ngly as precipitate; as precipitate;
Pb acid and then heat. filter; wash; dry filter; wash; dry
Cu (Al excepted)

Hg he at he at
Ag Oxides of these metals
} decompose when oxide of metal oxide of metal oxide of metal
Au heated.
(+ nitrogen (and water) (and carbon dioxide)
dioxide and
Aluminium oxide, AL0 3
oxygen)
This is a white solid. It is most conveniently prepared by first
adding dilute ammonia to an aluminium salt solution. This pre- Oxides of sodium and potassium, Na.X) and K2
cipitates aluminium hydroxide. These oxides are not much used laboratory or prepared in
in the
the usual course of experiment. They react vigorously with water to
Al,(SO«) 3 + 6NH 4 OH -> 2AJ(OH) + 3(NH«)t S0 4 3
form sodium and potassium hydroxides.
The precipitate is then filtered, washed, dried and heated.
NaaO + H,0 -* 2NaOH or O*- + H O ->- 20H"
s
2Al(OH) s -»• Al,0 3 + 3H,0
Calcium oxide (lime, quicklime), CaO
If prepared at the lowest temperature possible, it shows both basic
It is made in industry by the action of strong heat upon limestone,
and acidic properties:
calcium carbonate, the latter being placed in a kiln.
basic A1 3 + 6HC1 -> 2A1C1 8 + 3H,0
acidic Al,O a
2

+ 2NaOH + 3H 0-»- 2NaAl(OH)« CaC0 3 ->CaO + CO»

2
sodium 'The hydroxide and carbonate may also be obtained by adding sodium
aluminate hydroxide or sodium carbonate solution to a solution of any soluble salt of the
242 metal.
244 A NEW CERTIFICATE CHEMISTRY OXIDES 245

Very large quantities of calcium oxide are made in this way (Fig. sing as the water drops on the calcium oxide),
steam is formed and the
71). In the laboratory, calcium oxide can be made by placing a piece oxide cracks and puffs up and finally crumbles to a powder about
of marble in a crucible and three times as bulky. This is slaked lime (calcium hydroxide).
heating it strongly in a gas- CaO +H g
O-»-Ca(OH) t
heated muffle furnace. A high slaked lime
Firebrick temperature is required and
or
0»- + H tO-»-20H-
an hour or so is necessary to
AUow more water to fall on to the slaked lime until there is no
Lumps oF complete the action.
further action. If desired, at this stage, the mixture of slaked lime and
Limestone Class preparation of quick-
solution can be filtered and the filtrate shown to be lime-water by
lime. Make a loop in a stout from the lungs (containing carbon dioxide) through a
expelling air
iron wire large enough to
glass tube into the solution.
hold a piece of marble about
0t
(b) By
the action of dilute hydrochloric acid.
r the size of a P63 Place the
i¥f£/°
Lime
-
(i) On
the calcium carbonate. Effervescence is seen and the marble
piece of marble in the wire
finally disappears. Carbon dioxide is evolved, which, if passed into
and so arrange it on a tripod
lime-water, turns the latter turbid.
that when a Bunsen burner

Fio. 71. is placed underneath it, the

CaCOg + 2HC1 ->- CaCl* + H,0 + CO,
marble is just above the inner or CO g *- + 2H + -> H*0 + CO s
Continuous process for the
manufacture of lime. cone of the roaring Bunsen (ii) On calcium oxide. No evolution of carbon dioxide. The calcium
flame. (See Fig. 72.) Leave oxide will first give a similar action to (a ii p. 244) (slaking) but will
in this position for 5-10 minutes and then allow to cool until the give finally a colourless solution of calcium chloride.
solid can be comfortably held in the fingers. CaO + H tO^-Ca(OH) 8
The original substance (calcium carbonate) and the final product Ca(OH) a+ 2HC1 -> CaCl 2 + 2H s O
(calcium oxide) are very similar in appearance, both being white basic acid salt water
solids. The difference between them can be readily shown. hydroxide
Properties of calcium oxide. Calcium oxide is a white solid. It is

very refractory; that not melt even when heated to a very

is, it will
high temperature. It merely becomes incandescent and gives out a
powerful light. It was at one time used for this purpose (lime-light).
Iron Wire It reacts vigorously with water (see above) to form slaked lime,
VMMMSM/mtMWm/WM///fmt/i
7532 which is an alkali. Its solution in water is called 'lime-water'. Since
quicklime is basic in character and hygroscopic (that is, it absorbs
water) used to dry ammonia gas. It is used, after slaking, in the
it is

building trade to make mortar, for manufacture of sodium hydroxide

(p. 254), and for a very great number of operations needing a cheap
alkali.

Fig. 72.
Zinc oxide, ZnO
Calcining marble. This is a white powder (yellow when hot) made in in-
compound
dustry by distilling zinc and burning the vapour at a jet.
(a) By the action of water.
(i) On
calcium carbonate— no action. 2Zn + O g ->2ZnO
(ii) On
calcium oxide. Add water a drop at a time to the piece
of
or 2Zn + O a ->- 2(Zn* + 2 ")

calcium oxide in a dish. Great heat is developed (there

may be his- It is made in the laboratory from zinc by dissolving the metal in
 246 A NEW CERTIFICATE CHEMISTRY OXIDES 247

dilute nitric acid, evaporating the zinc nitrate solution

so formed It occurs naturally as magnetite and as such is a natural magnet or
to dryness and heating the residue strongly.
'lodcstone'.
3Zn f 8HN0 3 ->- 3Zn(N0 3) 2 + 4H 2 + 2NO On heating it in a stream of hydrogen it is reduced to iron (see

2Zn(N0 3) 2 -»- 2ZnO + 4N0 2 + 2 d. 158).

Zinc oxide is amphoteric (see p. 259). Fe 3 4 + 4H 2 ^ 3Fe + 4H O a

Zinc oxide (and the oxides already described) cannot be converted

Lead(U) oxide (litharge), PbO
into the metal by heating the oxides in a stream of hydrogen.
Zinc oxide, as 'zinc white', is used as a base in the paint industry. This is a yellow powder. It can be made in the laboratory by heating
lead dioxide, red lead, lead nitrate, lead carbonate
or lead hydroxide.
Although its 'covering power' is not so good as that of white lead
paint, it does not tarnish, as does a lead paint, on exposure (For details see compounds concerned.) It is best made from the
to air
which contains hydrogen sulphide. The reason is that zinc sulphide metal by the action of nitric acid with subsequent evaporation, and
is white whereas lead sulphide is black. heating of the lead nitrate. When prepared in the laboratory it usually
If there is any white paint in
ruins the test-tube in which it is prepared by fusing with
the glass. It
or near your laboratory, it will probably be a zinc paint. Otherwise
the hydrogen sulphide fumes would rapidly turn it dark is, in fact, used to make lead
glass— a glass of very high refractive
brown or
black. index.
Although lead(II) oxide can be considered a typical base, the only
common acid in which it will readily dissolve is nitric acid. The reason
lron(III) oxide, Fe 2 3 why it does not react quantitatively with the others is a purely
(Iron(II) oxide is not important.) This compound is mechanical one.
a red powder
known as 'jewellers' rouge'. It is used for polishing precious stones, Action of lead(ir) oxide on dilute sulphuric or hydrochloric acids.
and as a pigment. Lead(II) chloride and lead(II) sulphate are not formed quantitatively.
It is found in the impure state as haematite. Iron(III) oxide
These two substances are almost insoluble in water and, as the action
is made
in the laboratory: can only proceed on the outside of a particle of oxide, the lead(II)
(a) By heating iron(II) sulphate. chloride or sulphate forms as a layer on the outside. This layer of
(Note this action— it is a most
unusual type.) chloride or sulphate is not permeable to the acids and hence action
stops before any appreciable amount of the salt has been formed.
2FeS0 4 -*• FeiO s + SO, + S0 3 (For preparation, see under 'Chlorides' and 'Sulphates', and on
sulphur sulphur
p. 236.)
. . » ,
dioxide trioxide
(See p. 419.) Lead(II) oxide is reduced to grey metallic lead by heating
easily it

(b) By heating iron(IIT) hydroxide strongly. in a stream of hydrogen, coal-gas or carbon monoxide.

2Fe(OH) 3 ->-Fe 2 + 3H O PbO + H a -> Pb + H O a

Iron(lII) oxide also the product

3 a
PbO + CO -* Pb + CO a
is formed if iron(II)
hydroxide is
heated strongly in the air. All iron(II) compounds tend Lead(II) oxide is also an amphoteric oxide dissolving in alkalis to
to become form plumbites.
oxidised to lron(III) compounds by the oxygen of the
It has the usual properties of an oxide. It can
atmosphere.
NaOH + PbO + H aO -> NaPb(OH) 3 or Na + Pb(OH) 3 "
be reduced to metallic sodium
iron by being heated in a stream of hydrogen or carbon
monoxide. plumbitc
Fe 2 O a + 3H„ -»• 2Fe + 3H 2 Copper(ir) oxide (black copper oxide), CuO
Fe 2 O s + 3CO -* 2Fe + 3CO a
This is made in the laboratory by several methods which are given
with full experimental details on p. 243. Copper oxide is hygroscopic,
Tri-iron tetroxide (magnetic oxide of iron), Fe 3 absorbing moisture from the air. It is a basic oxide and dissolves
4

This compound may be prepared by readily in warm dilute mineral acid, forming copper(II) salts, e.g.,
passing steam over red-hot
iron (p. 265) or by burning iron in oxygen (p. 277). CuO + H SO«-> CuSO« + H O
2 t
248 A NEW CERTIFICATE CHEMISTRY OXIDES 249
If a solution of copper(II) oxide in concentrated hydrochloric acid
Lead dioxide (LeadfTV) oxide), PbO,
is gently boiled with clean copper turnings
in a fume-cupboard,
copper(II) chloride is reduced to copper(I) chloride (cuprous chlor- This oxide is a dark-brown powder and can be made in the labora-
ide). This precipitates (white) when the mixture tory in the following manner:
is poured into cold,
boiled-out water (which prevents re-oxidation). Into a beaker put some dilute nitric acid and warm it. By means of
a spatula, add red lead a little at a time. Care must be taken not to
CuO + 2HC1 -*• CuCl„ + H 2 add too much red lead or it will contaminate the product. As the red
CuCU + Cu -*-2CuCI lead reacts with the nitric acid, a brown powder is precipitated and
By a similar reduction, a copper(II) sulphate solution, mixed with lead nitrate is formed in solution. The mixture is filtered, the residue
sodium hydroxide solution and sodium potassium tartrate (to pre- washed two or three times with hot distilled
in the filter-paper is
vent precipitation of copper(II) hydroxide), precipitates red copper(I) water and is allowed to dry on the filter-paper, from which it may
oxide, or cuprous oxide, when warmed with glucose (a mild reducing then be shaken.
agent).
Pb 3 4 + 4HN0 3 -»- Pb0 2 + 2H 2 + 2Pb(NO,),
+ 40H- + C H 12 O + -f QH
2Cu*+ ->- Cu 2 2H 2 red lead lcad(IV) oxide lead nitrate
8 a 12 7

Heated copper(II) oxide is reduced to copper by hydrogen or carbon The properties of lead dioxide are summed up by the following

monoxide. experiments
(i) Action of heat. Heat a little lead(IV) oxide in a test-tube and
CuO + H 2 ->Cu + H a O or CuO + CO -* Cu + CO, hold a glowing splint in the mouth of the test-tube. The splint is re-
Like manganese(IV) oxide, copper(II) oxide catalyses the decom- kindled, showing the presence of oxygen. Litharge (lead(II) oxide)
position of potassium chlorate by heat. remains as a yellow solid, often fused into the glass.

Mercury(II) oxide, mercuric oxide, HgO 2Pb0 2 -*2PbO + 2

This red oxide yields, when heated, a mirror of mercury on the (ii)Action on concentrated hydrochloric acid. Warm a little lead(IV)
cooler sides of the test-tube, with oxygen evolved. oxide with concentrated hydrochloric acid. A
greenish-yellow gas
which bleaches litmus evolved (chlorine) and a white (often dis-
is
2HgO->2Hg + 1 coloured) solid, lead chloride, may be seen in the test-tube.

THE HIGHER OXIDES

Pb0 2 + 4HC1 - PbCl. + 2H 2 + Cl 2

(Compare manganese(lV) oxide.)

The higher oxides arc oxides which contain more oxygen per It will be seen from the above that lead(IV) oxide is an oxidising

molecule than the corresponding basic oxide. agent. If warm, it is converted by sulphur dioxide into lead sulphate
(a white solid) and the mass glows as combination takes place.
Sodium peroxide, Na 2 2 PbO, + S0 -* PbS0
2 4
This is made by heating sodium in excess of oxygen.
(iii) Action of hot concentrated sulphuric acid. Add lead(IV) oxide
2Na + 2
-»- Na 2 2 to concentrated sulphuric acid in a test-tube and warm gently. Effer-
It isa yellow powder and is a vigorous oxidising agent; it should vescence occurs, oxygen is evolved (test as in [i] above) and a white
never be allowed to come into contact with damp organic matter. precipitate of lead sulphate is left.
With water, it liberates oxygen. It is used in confined spaces, e.g., a 2Pb0 2 + 2H SO«-> 2PbS0 4 + 2H
2 2 + O,
submarine, where men are working, because it absorbs carbon
dioxide and liberates oxygen at the same time.
Red Pb 3
2Na 2 2 + 2H O -»- 4NaOH +
a 2
lead, triiead tetroxide, 4

2Na 2 2 2C0 — 2Na C0 3 +

-|-
2
»•
2 2 Red leadprepared by heating lead(II) oxide for some time in the
is

Sodium peroxide is a true peroxide, yielding hydrogen peroxide with presence of air at a temperature of 450°C.
dilute acids. 6PbO + 2
— »- 2Pb 3 4
250 A NEW CERTIFICATE CHEMISTRY
This compound, in many
chemical properties, acts as though it
consists of leadQI) oxide and Iead(IV)
oxide. For example, in the
experiment in preparing Iead(lV) oxide (p. 249):
Pb 3Q«4HNQ 8 -* 2Pb(NO a) a + 2H 2 + PbO,
-f

Compare 2PbO + Pb0 2 + 4HN0 3 > 2Pb(N0 3) 2 + 2H O + PbO,

a
Chapter 18
base I acid salt water
unchanged S
Or, in the action of heat:
Hydroxides
Pb 3 4 • 3PbO +O
2PbO + Pb0 2
-
• 2PbO + PbO + O
or more correctly Hydroxides of sodium
K "I Thehydroxidesof these metals are
2Pb a 4
—* 6PbO + O a Ca > soluble in water and are alkalis. and potassium not de-
Hence Na J (Also ammonium hydroxide.) composed by heat.
the action of heat on any oxide of lead is to leave lead(II)
oxide. Al "1
These metals form hydroxides'] Decomposition into
Red lead reacts with concentrated hydrochloric acid or concen- Zn which are insoluble in water. They oxide and water when
trated sulphuric acid when warmed to produce the same observed Fe are amphoteric, excepting
also hydroxides of these
[

effects as lead(lV) oxide (see above). Pb . the two hydroxides of iron. metals are heated.

Pb 3 4 + 8HC1 -» 3PbCl + 4H 2 2 + Cl 2 Cu Hydroxide is insoluble in water.

2Pb 3 4 + 6H S0 4 ->- 6PbS0 + 6H
2 4 2 +O a Hg "I Hydroxides of these metals do not
Red lead has been used for a long time as a pigment (the old name Ag \ exist.
for red lead, 'minium', gave the name 'miniature' to that type of AuJ
picture) and is used today, with oil, as a jointing material for gas and
Metallic hydroxides are electrovalent compounds, composed of
water pipes and in the manufacture of glass.
metallic ions, which are positively charged, and hydroxyl ions, OH~.
-
Manganese dioxide, Mn0 2 (Manganese(TV) oxide) The number of OH
ions associated with one metallic ion is equal to
the valency of the metal, e.g.,
See Oxygen (p. 273) and Chlorine (p. 355) for the common labora-
tory uses of this substance. It is also used in the glass industry.
Na + OH~; sodium is univalent
_
Ca 2f (OH ) 2 calcium is divalent
;

The metallic hydroxides form a very important series of compounds.

Questions on this chapter will be found on page 261. The soluble hydroxides (that the alkalis) are particularly im-
is,

portant. They have many uses both in the laboratory and industry.

Aluminium hydroxide, Al(OH) 3

This is a colourless, gelatinous solid. It can be precipitated by
adding dilute ammonia to a solution of an aluminium salt. The preci-
pitate is then filtered, washed and allowed to dry.

Al 2 (S0 4 ) a + 6NH OH->2Al(OH)

4 3
J
+ SfNHJjSO,
Amphoteric nature. If freshly prepared, the hydroxide is soluble in
forming a salt and water only, and so is basic.
dilute mineral acid,

Al(OH) 3 + 3HC1 -* A1C1 + 3H O

3 a
251
252 A NEW CERTIFICATE CHEMISTRY HYDROXIDES 253
It is alsosoluble in caustic alkali solution, again forming a salt and Since the properties are so nearly identical, the cheaper sodium
water only, and so is acidic. hydroxide is almost always used in preference.
AI(OH) 3 + NaOH-* NaAl(OH) 4
Sodium hydroxide (caustic soda), NaOH
Showing both basic and acidic character, it is amphoteric.
Sodium hydroxide is produced (at the cathode) by the industrial
From the above it is obvious that caustic alkali solution, when electrolysis of sodium chloride solution (brine). The anode product is
added to an aluminium salt solution, will react in two stages: chlorine. Since these products can react together,
(1) The production of a colourless, gelatinous precipitate of
20H- + Cl 2 -> CI- + OC1- + H 2
aluminium hydroxide.
they must be kept apart. In one form of cell (developed by Castner,
Al 2 (SO,) 3 + 6NaOH->2AI(OH) 3 j. + 3N a9S0 4 Kellner and Solvay) this separation is effected by the use of a circu-
(2) When the alkali is added in excess, this precipitate redissolves lating mercury diaphragm (Fig. 73). The circulation of the mercury
to give a colourless solution of sodium aluminate. brine
AI(OH) 3 + NaOH -»• NaAl(OH) 4 carbon chlorine spray
Uses. This hydroxide has the property of readily absorbing colour- jtj
|||
ing matter, e.g., if precipitated in a solution containing litmus, it will
give a blue 'lake' as precipitate. This makes
it useful as a mordant for

certain dyes. It will also carry down

bacteria from water and finds a brine
use in treating sewage. Precipitated in the fibres of cloth, it makes the
cloth waterproof.
cathode
Ammonium NH 4OH mercury distilled

^M^M
hydroxide,
hydrogen, water
This not strictly speaking a metallic hydroxide since the radical
is I II II-

(NH not a metal, nor has it been isolated. Ammonium hydroxide

4 ) is

solution is made by dissolving ammonia gas in water (see Ammonia,

p. 431, for fuller treatment).

NH 3 + H O->-NH OH
ammonIA
t
water ammonlUM
4
sodium
hydroxide
>m
J
sodium steel mercury
Y777,
hydroxide
It will turn red litmus blue and precipitate metallic hydroxides from
solution amalgam grids lift

solutions of salts of the metal. Fio. 73.

Manufacture of sodium hydroxide.
FeCl 3 + 3NH 4 OH Fe(OH) 8 J + 3NH 4 C1

It forms salts by the neutralisation of acids, for example, isshown heavily shaded. In the upper (brine) cell, sodium ion is dis-
charged and sodium enters the mercury forming sodium amalgam.
HNO + NH 4 OH -> NH 4NO g + H,0
a
ammonium nitrate
This occurs because hydrogen has a high over-voltage (0.78 volt) at
Action of heat. If ammonium hydroxide solution a mercury cathode and so does not discharge. Chlorine (an important
is heated, am-
monia gas and steam are evolved. by-product) is liberated at the anode.

NH OH->-NH 3 + H,0 At cathode At anode

4
Na+ + e~ -> Na Cl~ - e~ -*• $CU
Potassium hydroxide (caustic potash), KOH Sodium amalgam, flowing into the lower (soda) cell, encounters a
This is made in a similar manner
to that used for caustic soda. flow of distilled water in contact with steel grids on which hydrogen
Their properties are almost identical. Note that caustic potash is has only a very low over-voltage. Sodium hydroxide is formed and
much more soluble in alcohol than is caustic soda, and is used in in- hydrogen is liberated.
dustry to make soft soaps. 2Na + 2(H*OH-) -> 2(Na + OH) + H a
254 A NEW CERTIFICATE CHEMISTRY HYDROXIDES 255

Much sodium hydroxide is supplied to users (after concentration by

steam heat under reduced pressure) as a 47% solution. Further
evaporation by direct fire heat will give molten sodium hydroxide
which can be cast into solid pellets or sticks.
The high capital charge on the mercury used adds considerably to
the cost of this process and rival cells using asbestos separating
diaphragms, e.g., the Gibbs cell, have been tried. Here, the advantage
of cheapness is offset by the fact that sodium chloride penetrates the
diaphragm and pollutes the product.

Uses of sodium hydroxide

These uses are very extensive. The following are representative. Brine
(a) in soap manufacture. A fat or oil is boiled with aqueous sodium
hydroxide solution (p. 202).
(b) in the purification of bauxite. This purification yields pure
alumina, Alj0 3 for extraction of aluminium (p. 477).
,

(c) in the preparation of phenols and cresols from coal-tar. These

compounds are feebly acidic and are extracted from the tar by sodium Flowing mercury
hydroxide solution, cathode

e.g., phenol C,HsOH + NaOH ->• C H ONa + H O

8 s s

(d) in the textile industry. Sodium hydroxide

used in bleaching
is
and dyeing processes, in rayon manufacture and in mercerising
cotton to give it a silky sheen.

Illustration of Kellner Solva y cell

Fit up a burette with side tube as shown in Fig. 74. Adjust the taps
of the two burettes so that mercury flows at approximately the same
rate from each, and have a sufficient store of mercury in the upper
burette for about 20 minutes' flow. Connect the electrodes to a 12-volt Water
battery (or equivalent supply of electricity), drop a piece of red litmus
Fig. 74.
paper into water in the small beaker and arrange a piece of damp
Kellner-Solvay cell.
litmus paper so that gases from the anode come into contact with it.
After a few minutes, the piece of litmus paper in contact with the
anode gas is bleached (showing the presence of chlorine) and the (slaked lime) a little at a time and stir the mixture. A white solid
litmus paper in the beaker has turned blue showing the presence of forms on the bottom of the beaker. This is mainly calcium carbonate
an alkali. To show the evolution of hydrogen from the amalgam, fill together with some unattacked slaked lime.
the narrow tube with mercury and run oft* the bulk of the mercury NajCOa + Ca(OH), * CaC0 3 + 2NaOH
into water. A rapid evolution of hydrogen then takes place. sodium calcium calcium sodium
carbonate hydroxide carbonate hydroxide
Preparation of sodium hydroxide by Gossagc's method Filter off a portion of the contents of the beaker and, when the
3
beaker (of about 600 cm capacity) with water and add to
Half-fill a filtrate gives no effervescence with dilute hydrochloric acid, it is clear
it 30 g sodium carbonate as washing soda. Heat the solution almost that no sodium carbonate remains in it and the double decomposi-
to boiling and adjust the heating to keep it so. Add calcium hydroxide tion is complete.
256 A NEW CERTIFICATE CHEMISTRY HYDROXIDES 257

Filter the whole of the mixture and the liquid is a dilute solution of solution is strongly alkaline to litmus, turning it blue. Sodium
sodium hydroxide. The solid can be obtained from it by evaporation hydroxide will react with acids to form salts (see p. 233), for example
to dryness, preferably in an iron dish. with hydrochloric acid
NaOH + HC1 -*• NaCl + H„0
Slaked Lime sodium dilute sodium water
hydroxide hydro- chloride
solution chloric
acid

or OH- + H+ ^H 2

Action of gaseous acidic oxides on alkalis. As a general rule,

if a gaseous oxide (or hydrogen sulphide) is bubbled into any
I07o solution of alkaline solution, the final product is the corresponding acid
Washing soda
crystals in salt. (As a rule the normal salt is first formed but it is diificult
' water to isolate inmost cases.)
Thus when sulphur dioxide, hydrogen sulphide or carbon
dioxide are bubbled for some time into potassium hydroxide
solution, sodium hydroxide solution, lime-water or ammon-
ium hydroxide, the product is the acid salt; for example:
CO g + NaOH -* NaHCO a
sodium hydrogen
carbonate
H 8S + KOH ->• KHS + H aO
potassium
hydrogen
Fio. 75. sulphide
Preparation of sodium hydroxide from sodium carbonate. Ca(HS0 3) 9
2SO* + Ca(OH) 2 -»-
calcium hydrogen
Preparation of sodium hydroxide by the action of sodium on water sulphite

This described on p. 196.

is The normal salt can usually be made by the addition of the same
A dilute solution of sodium hydroxide can be obtained by placing weight of alkali as was taken at the commencement of the operation,
very small pieces of sodium on water. for example:
2Na + 2H gO -* 2NaOH + H 2
H 8S + KOH -> KHS + H g O
Properties. Sodium hydroxide is a white solid. It is very deli- KHS + KOH -» K,S + H a O
potassium
quescent, has a soapy feel, and will corrode the skin. Care should be sulphide
used in handling the solid and its solution. (See p. 400 for experimental details.)
Action on exposure to air. Leave a small piece of sodium hydroxide Sodium hydroxide as a hydroxide-former. The majority of the metal-
on a watch-glass exposed to the atmosphere for a few days. There is lic hydroxides are insoluble in water, and as we shall see in the
formed a solution of sodium hydroxide, showing the solid to be deli- remainder of this chapter, the usual method of making a hydroxide is
quescent. Finally, a white crystalline crust of sodium carbonate is
to add sodium hydroxide solution to the solution of a soluble salt of
formed by the action of the carbon dioxide of the atmosphere. the metal, and isolate the product as described in Chapter 18.
Action with water. All deliquescent substances are very soluble in Action of sodium hydroxide on ammonium salts. If any ammonium
water. As sodium hydroxide dissolves, a great amount of heat is
salt is boiled with sodium hydroxide solution ammonia gas (turns
red
liberated and the solution should always be made in a thin vessel, liberated.
litmus blue) is
otherwise the glass may be cracked.
NH«C1 + NaOH -> NaCl + H,0 + NH,
Action of sodium hydroxide as an alkali (that is, a soluble base). The
or NH + + OH" -* NH + H ,0
4 3
258 A NEW CERTIFICATE CHEMISTRY HYDROXIDES 259

Calcium hydroxide (slaked lime), Ca(OH) 8 mass of interlacing crystals of great strength. Some
water, sets to a
This is a white solid not nearly so soluble in water as sodium or cements even under water. When mixed with gravel or brick
will set
potassium hydroxide. rubble, cement forms concrete, and is used with water in the same
Preparation. It is prepared commercially and in the laboratory by way.
the action of water on calcium oxide (which is obtained by the action
Zinc hydroxide, Zn(OH) 8
of heat on limestone).
CaO + H,0 -»- Ca(OH) 8 Thisa white powder. It is formed as a white precipitate when
is

calcium sodium hydroxide solution is carefully added to the solution of a

hydroxide soluble zinc salt (usually zinc sulphate).
(See p. 244 for experimental details.)
ZnS0 4 + 2NaOH ->- Zn(OH) 8 -1- Na 8 SO,
Properties. Slaked lime is a white solid. Lime-water is formed when
slaked lime is dissolved in water, but its solubility is only very small or Zn2+ + 20H- -»- Zn(OH),
(about 0.14 g in 100 g water at 20°C). The whiteprecipitate, if required, may be filtered off, washed with

This solution is, however, definitely alkaline and will give the hot distilled water and dried on a porous plate.
usual
reactions of an alkali. Amphoteric nature of zinc hydroxide. Care must be taken in the
Action of heat on calcium hydroxide. Strong heat will convert slaked above experiment not to add excess sodium hydroxide solution, since
lime into quicklime. In the laboratory the experiment is performed in zinc hydroxide is soluble in excess of caustic alkali solution,
forming
a fireclay furnace by the identical method used to convert calcium a zincate.
Zn(OH) 2 + 2NaOH - Na^nfC-H),
carbonate into quicklime (see p. 244).
Ca(OH) 8 -> CaO +H 8
or Zn(OH) 8 + 2C-H" - Zn(OH)««-
with the
Action of carbon dioxide on lime-water. Lime-water is used as a Here zinc hydroxide is acting with acidic properties because,
test sodium zincate, and water.
for this gas owing to the fact that a white precipitate of chalk is alkali sodium hydroxide, it forms the salt,
hydroxides, zinc hydroxide has basic properties
formed on bubbling carbon dioxide into lime-water. Like most metallic
also, and it reacts, for example, with dilute
sulphuric acid to form the
Ca(OH) 8 -f CO s -»- CaC0 3 + H,0 salt, zinc sulphate, and water.

A milkincss
calcium
carbonate Zn(OH) 2 + H S0 4
8
- ZnSC- 4 + 2H O a
water
produced which is caused by small particles of solid
is base acid salt

chalk. Further passage of carbon dioxide produces calcium hydrogen

A metallic hydroxide which exhibits both basic and acidic properties
carbonate, which is soluble in water (see p. 206). The corresponding oxides are also am-
is said to be amphoteric.
Uses. Calcium hydroxide is used in the manufacture of mortar and photeric. .
bleaching powder and is also used by farmers to counteract acidity Action of heat. Zinc hydroxide is readily converted into zinc oxide
on the land. by the action of heat.
Mortar is made by mixing calcium hydroxide, sand and water. The Zn(OH) 8 -vZnO +H 2
settingis due to the giving up of surplus moisture zinc
and for this reason
oxide
new houses are always damp for some time. With the passage of
(yellow hot,
years some of the calcium hydroxide is converted into calcium white cold)
car-
bonate by carbon dioxide from the air.
Hydroxides of iron, Fe(OH)i!, Fe(OH) 8
Ca(OH) 2 + CO s
-»- CaCO, +HO hydroxide and iron(III)
Iron forms two hydroxides, iron(II)
a
Hence, an old mortar will give an effervescence with dilute
acids, hydroxide.
whereas a new mortar will not. ,
action of sodium hy-
.

Iron(U) hydroxide is precipitated by the

CaC0 3 + 2HC1 ->- CaCl 2 + H 8 + CO a droxide solution on iron(II) sulphate solution.
Cement is made by strongly heating limestone and clay together. FeS0 4 + 2NaOH->- Fe(OH) 8 | -f Na sS0 4
The cement is powdered and, after mixing with a suitable amount of or Fe2+ + 20H--»-Fe(OH) 8
 260 A NEW CERTIFICATE CHEMISTRY QUESTIONS 261

excluded the substance is white, but under ordinary con-

can be obtained as a blue powder by filtering off the precipitate,
If air is
ditions it is seen as a dirty-green gelatinous precipitate. It is trouble- washing it several times with cold distilled water and allowing it to
some to isolate the solid, as it is so readily oxidised by the air. Make
dry.
the precipitate in the way indicated above and allow it to stand or
CuSO« + 2NaOH ->- Cu(OH) + Na 2 2 SO,
warm it.be seen to turn reddish brown because it is oxidised
It will
Cu*+(aq) + 20H "(aq) -»• Cu(OH) 2 (c)
or
by the oxygen of the atmosphere to reddish-brown iron(III) hy-
It is soluble in dilute acids forming solutions of copper(II) salts. For
droxide.
example,
4Fe(OH) 1 + O s + 2H aO -* 4Fe(OH)
+ H S0 -> CuS0 4 + 2H O
3
Cu(OH) 2 2 4 g
For the same reason, on heating ironfjl) hydroxide strongly, iron(Ili)
oxide remains. On warming the hydroxide, it readily loses water and forms black
Jron(IJI) hydroxide
precipitated as a reddish-brown gelatinous
is copper oxide (see p. 26).
precipitate by adding an alkaline solution (for example, sodium Cu(OH) 3 -»- CuO + H 2
hydroxide solution) to a solution of iron(III) chloride.
Copper(II) hydroxide dissolves in ammonia to form a deep blue
FeCIg + 3NaOH -> Fe(OH) + 3 3NaCI solution. This blue solution will dissolve cellulose (for example, a
or Fe8 + + 30H- —* Fe(OH) 3 filter-paper) and this solution of cellulose has been used to make
To purify wash well with hot distilled water artificial silk by forcing the solution through tiny holes into an acid
it, filter off, and allow it

to dry. solution. The fibres so formed are spun into threads.

On heating the hydroxide strongly, iron(III) oxide is obtained as
a red powder. QUESTIONS
2Fe(OH) s -»- Fe s 3 + 3H O s
1. Describe a method for Ihe preparation of sodium hydroxide
from
Ironfjl) and iron(III) hydroxide dissolve in dilute acids with the
sodium chloride.
formation of salts and water, thus indicating their basic nature. Give an account of the reaction of sodium hydroxide with (a) carbon
dioxide; (b) zinc; (c) a solution of zinc sulphate.
Lead(D) hydroxide, Pb(OH), Give the equations in each case. (C)
This is formed as a white precipitate by adding sodium hydroxide 2. Sulphur dioxide is called an acidic oxide and copperfjl) oxide a basic
solution cautiously to lead nitrate solution. oxide. What is meant by these terms? Give two other examples of each of
these classes of oxides and describe how you would test an oxide in order
Pb(N0 3) 2 + 2NaOH -> Pb(OH) + 2NaN0 to assign it to one of these classes. (O. and C.)
or Pb a+ (aq) -
+ 20H~(aq) Pb(OH) (c)
2

2
3
3. chemical properties distinguish metals as a class? Describe in
What
Itcan be obtained as a white powder by filtering off, washing with hot detail threemethods by which a metal may be converted inlo its oxide. In
each case name the metal which you would use. (L.)
distilled water,and allowing it to dry.
4. How would you obtain from calcium carbonate pure specimens of
Like zinc hydroxide it is amphoteric and will dissolve in acids to
(a) calcium oxide; (b) calcium hydroxide? Describe the properties of an
form lead(II) salts and in alkalis to form plumbites. aqueous solution of calcium hydroxide, explaining what changes occur
Pb(OH) 2 + 2HNO s -
PbfNO^j + 2H 2 when carbon dioxide is passed through the solution. (O. and C.)
5. Name five gases which can be absorbed by sodium hydroxide. Explain
Pb(OH) 2 (c) + OH-(aq)-> Pb(OH) 3 -(aq)
the reactions which take place on absorption, and in each case give one
plumbite ion
test by which you could recognise the product. (L.)
On strongly heating lead(II) hydroxide, Iead(II) oxide remains as 6. How may lead(II) oxide and lead(lV) oxide be obtained, starting from
a yellow powder. metallic lead ?
Pb(OH) 2 -»-PbO +H 2
Describe how you would show by experiment that their composition is
in agreement with the Law of Multiple Proportions. (L.)
Copper(II) hydroxide, Cu(OH) 2 7. What is the chemical nature of galena and white lead? Starting with
red lead (PbjOi), how would you prepare a specimen of each of the
This is formed as a blue gelatinous precipitate on adding sodium following; (a) metallic lead; (6) lead(II) oxide; (c) lead(TV) oxide?
hydroxide solution to cold copper sulphate solution. The substance (N.U.J.B.)
 .

262 A NEW CERTIFICATE CHEMISTRY

8.Explain the meaning of the terms base, basic oxide, hydroxide.
Classify the following substances: lime, ammonia, caustic soda. Give
reasons for your classification. (O. and C.)
9. Define base, hydroxide, alkali, giving two examples of each with
formula. Indicate briefly how you would prepare (a) sodium hydroxide,
using sodium carbonate; (b) iron(TIl) hydroxide, using iron(IU) chloride.
(N.U.J.B.)
Chapter 19
10. What do you understand by (a) a base; (6) an alkali?
Draw a labelled diagram to show how sodium hydroxide is prepared
electrolytically. (The diagram should show the nature of the electrolyte
and all products, the names, signs and materials of the electrodes, and any Hydrogen
other details essential to the process.)
Stateconcisely what you would observe when a stick of sodium hydroxide
is left exposed to the air for a long time. (Equations are not required in this
question.) (N.U.J.B.) K
1 1 What are the four chief classes of oxides ? Give one example of each Ca
class. Na Dilute sulphuric and hydrochloric acids attack these metals
How do oxides of metals differ chemically from those of non-metals? Mg \ with the liberation of hydrogen.
State briefly how you would prepare from suitable oxides (a) a solution (Al with dilute HC1 only)
Al
of copper(II) sulphate; (6) a dilute solution of hydrogen peroxide.
What happens when manganese(IV) Zn
oxide is added to a solution of
hydrogen peroxide? (N.U.J.B.) Fe
Pb
(H)
Cu
Hg
Ag
Au
Hydrogen was first recognised by Cavendish (1766). It was called
'inflammable air', and the name hydrogen {i.e., water producer) was
given to it by Lavoisier.

Occurrence
Uncombined hydrogen does not occur in nature to any appreciable
extent, but the element occurs in vast
quantities in a combined state

in such compounds as water, acids, and many organic substances.

Industrial preparation of hydrogen

Hydrogen has acquired much greater importance in recent years

because of new uses given below. There are now two chief
methods
of manufacture— from hydrocarbons and by electrolysis.
years, hydrogen has been made
(1) From hydrocarbons. In recent
almost entirely from hydrocarbons. To use the simplest
example,
catalyst
methane (natural gas) can be passed with steam over nickel
at 800°C and 30 atm.
CH 4 +H O->-CO +
t 3He
The product is mixed with more steam and passed over iron(IH) oxide
263
264 A NEW CERTIFICATE CHEMISTRY HYDROGEN 265

(catalyst) at 450°C. Carbon monoxide is converted to the dioxide with Dilute Sulphuric
further yield of hydrogen. 1 Acid
CO + 3H 2 + H 2 ->- C0 + 4H
2 2

Carbon dioxide is dissolved out by water under 30 atm pressure.

H,0 + CO, ^ H C0 2 3
Hydrogen

Any remaining traces of carbon monoxide are absorbed under pres-

sure, by copper(I) formate in ammonia.
(2) By Hydrogen is obtained as a by-product in the
electrolysis.
electrolytic manufacture of sodium hydroxide from common salt Zinc
(p. 253).
Where electrical power is cheap, hydrogen can be made by elec-
trolysis of water containing sulphuric acid. The laboratory version of
Fig. 76.
this method is fully discussed on p. 146.
Preparation of hydrogen.
Uses of hydrogen
effervescence, and a gas is given off which is collected over water, as
(1) For filling balloons. It is the lightest gas known but has the
shown in Fig. 76. Zinc sulphate, which is formed, dissolves in the
great disadvantage of inflammability.
water to form zinc sulphate solution.
(2) In the 'hardening" of oils to make margarine. Oils, e.g., olive oil
or whale-oil, are heated to 180°C and finely divided nickel is added Zn + H 2 SO,-»- ZnSO, + H a
as catalyst. They are then treated with hydrogen at about 5 atm or Zn + 2H 80+ -> Zn* + + 2H.O + H,
pressure. The oil combines with hydrogen and is converted to a fat, Hydrogen from water. Action of steam on heated iron
which is solid at ordinary temperature and is used in the manufacture
This method is very suitable for obtaining hydrogen in quantity.
of margarine. In this way, a liquid oil, unacceptable in our diet, is
The apparatus consists of a long iron tube loosely filled with iron
'hardened' to an acceptable solid fat and used as a butter-substitute.
(3) In the conversion of coal to synthetic 'petrol'. A paste of coal- Safety tube
dust and oil, containing iron oxide and alkali as catalyst, sprayed
is
Iron nails and Filings
into hydrogen at 200 atm pressure and 450°C. The products are
hydrocarbon gases and a liquid oil. On distillation, this oil yields a
fraction suitable for petrol. (This process has been made obsolete
by large, cheap supplies of natural petroleum.)
(4) In the manufacture of ammonia. This is Haber's Process, des-
cribed on p. 431. Hydrogen
(5) In the synthesis of hydrochloric acid (H 2 + Cl 2 —* 2HCI) and
of organic chemicals, e.g., methanol, CH 3OH. Also in the oxy-
hydrogen flame for cutting and welding steel.
V
Preparation of hydrogen by the action of dilute acids on metals
Note. Hydrogen explodes violently with air if a spark or
flame reaches the mixture. For safety, always collect a
sample of hydrogen and test as described on p. 47 before
lighting a jet or collecting the gas in bulk.

Into a flat-bottomed flask or bottle, put some pieces of zinc and Fio. 77.
add dilute sulphuric acid by means of a thistle funnel. There is Preparation of hydrogen in quantity from steam.
 266 A NEW CERTIFICATE CHEMISTRY PROPERTIES OF HYDROGBN 267

filings and
nails which arc heated to redness by a furnace (Fig.
77). bubble the gas into a gas-jar containing about two thirds of its volume
Steam is all displaced. Apply a
generated by boiling water in a can, and the steam passes
is
of air, passing in hydrogen until the water
over the heated iron, forming hydrogen, which is collected to the mixture and there is an explosion.
over flame
water. Any excess steam condenses as it comes into contact with 2H a + -»-2H a O
the 1
cold water. The iron is converted into tri-iron tetroxide (black oxide
Hydrogen a reducing agent. Hydrogen readily reduces the oxides
is
of iron).
they are heated in a stream
of copper, lead or iron to the metal when
3Fe + 4H O -* Fe 3
a 4 + 4H 2 (see p. 48),
iron steam tri-iron hydrogen of the gas, i.e.

tetroxide CuO + H 2 -*Cu + H a O

This reaction is reversible (see p. 158). PbO + H a ->Pb + H aO
Fe 2 3 + 3H a -»- 2Fe + 3H aO
Hydrogen from alkalis hydrogen makes electrons
In these cases, the system of oxide ion and
Warmsodium (or potassium) hydroxide solution will react with available and so acts as a reducing agent.
zinc, aluminium or silicon to liberate hydrogen and leave a solution 2
--r-H a ->H aO + 2e-
of sodium (or potassium) zincate, aluminate or silicate.
metallic ion acts as an oxidising agent by accepting the electrons
The
Zn + 2NaOH + 2H O -»- Na Zn(OH)« + H,
a a and is reduced to the corresponding metallic atom.
2A1 + 2NaOH + 6H aO -* 2NaAl(OH) + 3H
Si + 2NaOH + H O -> Na^SiOa + 2H
4 2 Cu* + + 2e~ -* Cu (Pb similar)
a a 2Fe3+ + 6e- -» 2Fe
These methods are not usually used
Nascent hydrogen. A system of acid and metal which
in the is generating
laboratory. very vigorous
hydrogen, e.g., zinc and dilute hydrochloric acid, has a
Test for hydrogen. A mixture of hydrogen and air ion in solution
reducing action. For example, it will reduce iron(Ui)
explodes when a flame is applied. passed through the iron(III)
to iron(H) ion, though gaseous hydrogen
ion solution does not reduce the ion at all. The reducing action used
Properties of hydrogen
ascribed to so-called nascent hydrogen, i.e., hydrogen at the
to be
Hydrogen is an invisible gas, neutral to litmus,
of its chemical production, which was assumed to be
very
and,
moment
if pure, possesses no
This conception has been abandoned. The prevailing idea
smell.
reactive.
Hydrogen is lighter than air. Hold a gas-jar full electropositive metal,
now is that, in the presence of the acid, a fairly
of hydrogen (B) under a gas-jar full of air (A) and
e.g., zinc, makes electrons available; that is, it acts as a reducing
take off the cover (see Fig. 78). oxidising agent, iron(UI)
agent. The electrons are accepted by an e.g.,
Fio. 78. Count ten. Now apply a lighted splint to the
and reduced— in this case to ironfjl) ion.
in it
gas-jar which previously contained air, and the gas
will burn or explode, showing hydrogen has passed upwards
ion, it is

Zn -Zn* + 2e~ +
into it. On
applying a flame to the gas-jar which originally con-
2Fea+ + 2e--*2Fe il+

Adding these, Zn + 2Fe s+ -> Zn* + + 2Fe* +

tained hydrogen, the flame produces no change, showing the gas to
conditions are
be air. Sources of the so-called nascent hydrogen in alkaline
Hydrogen burns in air. Invert a gas-jar of hydrogen and apply a sodium amalgam and water, or aluminium and sodium hydroxide
The gas burns cases, also, the mixtures act as reducing agents by
lighted splint. quietly round the edges of the gas-jar. solution. In these
A splint pushed up into the gas will be seen to be extinguished.
Hence making electrons available.
hydrogen will burn in air but will not allow a splint to burn in it. NaHg->-Hg-r-Na + -f-e-
The product of the combustion of hydrogen is water. Al + 40H- -
Al(OH)r + 3e~
2H a +O a -*2H 2 Action of hydrogen on the halogens. Hydrogen
combines with
Hydrogen explodes chlorine to form hydrogen chloride,
if mixed with air and a flame is applied. (The
usual test for hydrogen.) When collecting the hydrogen over water, H +Cl a a -»-2HCl
 268 A NEW CERTIFICATE CHEMISTRY PROPERTIES OF HYDROGBN 269

with bromine, less readily, to form hydrogen bromide This can be shown by the simple apparatus depicted in Fig.

H, + Br a ->-2HBr 79.

with iodine, less readily still. (See Halogens.) To show the rapidity with which hydrogen diffuses. A porous pot has a
rubber stopper which fits tightly in its mouth and is connected to a bent
Isotopes of hydrogen glass tube containing coloured water (Fig. 79).
A beaker surrounds the pot and coal-gas is passed into the beaker by
This subject is, in the main, beyond the scope of the present book. placing an unlit Bunsen burner under it and turning on the gas tap. On
It may be briefly mentioned, however, that hydrogen has at least doing so, the level of water in the limb directly below the pot begins to fall
three isotopes— ordinary hydrogen or protium, H, heavy hydrogen or because the coal-gas (which contains about half its volume of hydrogen)
deuterium, D, and tritium, T. All these have one electron per atom. diffuses through the tiny pores of the pot more quickly than the air diffuses
out of the pot. This causes an excess pressure of gas in the pot, making the
In protium, the nucleus of the atom consists of a single proton; in few moments,
level fall. When the level returns to normal, as it will do in a
deuterium, the nucleus contains a proton and a neutron; in tritium, it the beaker containing the coal-gas is removed. Now the reverse happens
contains a proton and two neutrons. The approximate atomic weights and the level of the water in the shorter tube rises. This is because the coal
are, therefore, H= 1, D =
2 and T =
3. Protium and deuterium
gas (now inside the pot) diffuses out more rapidly than the air can diffuse in,
resemble each other closely in chemical behaviour, deuterium being and causes a lowering of the pressure inside the pot, and hence the level
rises
somewhat less reactive. Deuterium oxide is known as heavy water, Graham found that the rate of diffusion of a gas was inversely propor-
D 2 0. It resembles ordinary water but has a higher density (about tional to the square root of its density in constant conditions. For example,
1.10 gem
-3
at room temperature). Tritium is radioactive; it has a since the density of oxygen relative to hydrogen (T. and P. constant) is 16,
half-life of about twelve years— that is, in that time, half of the Rate of diffusion of hydrogen = V16 = 4
tritium is lost by conversion into the products of the radioactive Rate of diffusion of oxygen VI 1

change.
Diffusion
Invert a gas-jar of hydrogen over a gas-jar of air the hydrogen
(i.e.,
is the uppermost of the two). Remove the plates and leave for ten
minutes. Plunge a lighted taper
into each gas-jar separatelyand
in both cases there is an explo-
sion, showing hydrogen to be
present in quantity in both of
the gas-jars. Hence some of the
hydrogen must have descended
from the upper gas-jar to the
\ Level
lower. This seems contrary to
the result of the experiment
above which shows the gas to
be less dense than air.
Co/oured
f/aattt
This process of filling the
That is, hydrogen diffuses four times as rapidly as oxygen. This may be
applied as a method of rinding the molecular weight of a gas by finding its
vapour density from its rate of diffusion.
All gases, diffuse, i.e., they attempt to distribute themselves uniformly
throughout the containing vessel. For example, if a gas-jar of (brown)
bromine vapour (density relative to hydrogen = 80) is placed below a gas-
jar of hydrogen, the bromine diffuses upwards and the hydrogen downwards
until a uniform brown colour is seen throughout the gas-jar. Similarly (but
very much more slowly), if a large crystal of (blue) copper sulphate is put
into a gas-jar which is then about half-filled with water and left to stand
(covered), the salt will dissolve and its ions will diffuse upwards while water
molecules diffuse downwards till a uniformly blue solution is obtained.
The burning of hydrogen in air to form water
This is the synthesis of water, i.e., the building-up of water from its
elements.
Fitup the apparatus as shown in Fig. 80.
Hydrogen is generated by the action of dilute hydrochloric acid on
zinc.
Zn + 2H+ -> Zn 8+ +H s

whole of a vessel inwhich a The gas then passes through a U-tube containing calcium chloride in
gas is placed is termed dif- order to dry the gas, the hydrogen is burnt at a jet, and the vapours
fusion. Hydrogen diffuses (i.e., are cooled by coming into contact with a can kept cool by water.
spreads throughout the vessel When the apparatus has been set up (use rubber stoppers or very
Fig. 79. in which it is placed) more
well-fittingbark corks), place a test-tube over the jet and collect a
Coal-gas diffuses more rapidly than rapidly than any other gas.
air.
test-tube full of hydrogen by displacement of air. When this test-
270 A NEW CERTIFICATE CHEMISTRY QUESTIONS 271

tube full of gas burns quietly on the application of a flame to it, CuS0 4 + 5H 2 = CuS0 4 .5H 2
light the jet and allow the flame to burn so that it just does not touch blue vitriol

the cooled can. 2. Boiling-point (see Fig. 81).

If the atmospheric pressure is 760 mm, the thermometer should
Bright metal can
register 100°C.
These two tests togetherprove the liquid to be pure water. An
additional, but less convenient test, is to find the freezing-point,
which should be 0°C at 760 mm pressure.
2H, + = 2H O
2 s
from
Co/our/ess
liquid

Calcium Chloride QUESTIONS

to dry the.
Hydrogen 1 What weight of sulphuric acid would be necessary to react with zinc
hydrogen to fill 6 gas-jars, each containing 400 cm
3
to provide sufficient
Zinc and dilute at 15°Cand750mm?
Hydrochloric acid
Hydrogen is a reducing agent. Illustrate this statement by reference
2.
Fio. 80.
to the action of the gas with (a) oxygen; (b) chlorine; (c) copperfM) oxide.
Synthesis of water.
3. If a mixture of hydrogen and oxygen is passed slowly through a long
porous tube the gas issuing at the other end does not explode when a flame
Moisture will condense on the can and will drop off into a dish is applied. Explain this. If the same experiment was
performed with a
which is placed below to receive the liquid. mixture of carbon monoxide and air, would you expect the gas issuing at
The liquid can be shown to be water by the tests described below: the end to explode or burn when a flame is applied ? Give reasons for your
answer.
4. Describe two methods by which you could prepare reasonably pure

- 100'C If A.P.
hydrogen. . .

Slit fortscope is 760mm. Calculate (a) the volume; (Z>) the percentage composition of the gas
of vapour \
which remains when equal volumes of air and hydrogen are exploded and
the products are allowed to cool down to room temperature again. (Air
contains 21% of oxygen by volume.) (O.)
5. By what properties could you distinguish between the
compounds
which hydrogen forms with (a) chlorine; (b) sulphur; (c) nitrogen? Sketch
Cotton-wool to prattel
tht bulb from the apparatus you would employ to prepare and collect a sample of one of
suptr-fieat/ny these compounds. (N.U.J.B.)
6. would you prepare dry hydrogen, and show that it forms a
How
liquid when burned in air? Draw the apparatus you would use. By what
-l/au/d for lest experiments could you show that the liquid (a) contained water; (6) con-
tained nothing but water? Give full details. (N.U.J.B.)

Fig.

1. Action on anhydrous copper sulphate.

Allow a drop of the liquid to fall on to anhydrous copper sulphate.
A blue patch on the white solid (with hissing and development of
heat) proves water is present, but does NOT prove the liquid to be
pure water.
 OXYGEN 273

weight of oxygen in a combined state in the form of water, silicates,

many metallic and non-metallic oxides, and in the form of
salts.

Chapter 20 Laboratory preparation of oxygen from potassium chlorate

Crush some potassium chlorate crystals (20 g) in a mortar and
grind with them about one-quarter of their weight (5 g) of man-
ganese dioxide (manganese(IV) oxide). Place the mixture in a hard-
Oxygen glass tube and fit up the apparatus as shown (Fig. 82). Heat the
K mixture and a gas will readily be given off which can be collected
Ca over water.
Na
Since oxygen has about the same density as air, it cannot
Mg When heated in air these metals oxidise with a readiness
be collected by displacement of air. If required dry it can be
Al indicated by the order shown; that is, potassium most
dried by calcium chloride and collected over mercury.
Zn easily, copper least readily.
Fe Potassium chloride is left in the tube.
Pb 2KC10 3 ->-2KCl-}-30 2
Cu or 2C10 3 -->-2Cl- + 30 2
Hg | These metals do not oxidise easily; their oxides yield
Ag Test for oxygen
f oxygen on heating.
Au It rekindles a glowing splint of wood. This distinguishes

Oxygen was
it all gases except dinitrogen oxide,
from a O. It is distin- N
discovered by Scheele in 1772, but Priestley dis-
first
guished from this gas:
covered it independently two years later by heating oxide of mercury.
(a) by having no smell (dinitrogen oxide has a sweet, sickly
He it 'dephlogisticated air', but Lavoisier called it oxygen
called
smell).
(acid-producer) because he obtained acids by heating several non-
(b) with nitrogen monoxide, oxygen produces brown fumes of
metals in oxygen and dissolving the oxides in water.
nitrogen dioxide.
Occurrence 2NO + 2
->2N0 2
Uncombined oxygen forming 21% by volume (or
exists in the air, nitrogen
dioxide
23% by weight). The earth's crust consists of almost half of its
Dinitrogen oxide has no effect on nitrogen monoxide.
Potassium
Chlorate 4
Manganese Manganese dioxide (manganese(TV) oxide) as a catalyst
Dioxide I
potassium chlorate is heated alone, it gives off oxygen, but only
If
at fairly high temperature (400°C). If mixed with manganese
a
dioxide, the potassium chlorate gives off oxygen at a much lower
temperature and much more steadily. On analysis of the residual
mixture, it is found that the amount of manganese dioxide is exactly
the same at the end of the experiment as it was at the beginning.
A substance which can alter the rate of a chemical reaction in
this way is called a catalyst.
Definition. A catalyst is a substance which, although present in small
Fig. 82.
proportions, alters the rate of a chemical reaction, but remains chemi-
Preparation of oxygen from potassium chlorate.
cally unchanged at the end of the reaction.
272
274 A NEW CERTIFICATE CHEMISTRY OXYGBN 275

Class experiment to show manganese dioxide is a catalyst An alternative preparation (in the same apparatus) is the drop by
Mix a manganese dioxide with about four times its bulk of
little drop addition of hydrogen peroxide solution (20 vol.) to potassium
potassium chlorate and place in an ignition tube. Into each of two permanganate in the presence of excess of dilute sulphuric acid.
other tubes put an approximately equal bulk of manganese dioxide Oxygen is liberated until all permanganate is decomposed, by which
and potassium chlorate respectively. Surround each with sand on a lime the mixture is colourless.
sand tray so that they are close together and vertical. (See Fig. 83.) 5H,0, + 2KMn0 4 + 3H,SO«-»- K 2 S0 4 + 2MnSO t + 8H.O + 50,
Commence to heat and test at intervals for oxygen by lowering a
glowing splint into each test-tube. After about one minute oxygen is 20 vol.
freely evolved from the mixture, with no signs of gas from either of hydrogen
the other tubes. peroxide
In order to be quite certain that the oxygen was coming from the
oxygen
solution
chlorate and not merely from the manganese dioxide, it would be
necessary to show that the weight of manganese dioxide was the same
Water
after theexperiment as before it. This could be done by dissolving manganese
the chlorate and chloride of potassium in water and recovering the
dioxide
manganese dioxide by filtering, washing with water, and drying in a
steam oven. It would be found that there was no appreciable loss of
weight. For further discussion of catalysis, see p. 155. Fig. 84.
Preparation of oxygen from hydrogen peroxide.

Potassium
Chlorate. Properties of oxygen

Oxygen is a colourless, odourless, neutral gas, is almost insoluble

/Va/jyanese Mixture of in water and has approximately the same density as that of air. It is
Dioxide *-s 6otf>
an exceptionally active element, combining vigorously with many
metals and non-metals, forming basic and acidic oxides respectively:

METALS + OXYGEN •
METALLIC OXIDES most of which
Sand are basic
in character
NON-MBTALS + OXYGEN -* NON-METALLIC OXIDES most of
which are
ACIDIC
in character

Fio. 83. Action of oxygen with non-metals to form acidic oxides

To show manganese dioxide is a catalyst. Phosphorus. Place a small piece of yellow phosphorus in a defla-
grating spoon, warm it until it begins to burn, and then plunge it into
Laboratory preparation of oxygen from hydrogen peroxide a gas-jar of oxygen (Fig. 85) into which you have previously poured
This is a convenient preparation because it requires no heat. a little blue litmus solution. The phosphorus burns with a dazzling
Hydrogen peroxide solution (20 vol.) is added, drop by drop, to flame, emitting white clouds of oxides of phosphorus which dissolve
manganese dioxide, which catalyses decomposition of the peroxide. in the water to form acids of phosphorus, which turn the litmus red.
Oxygen is collected over water (Fig. 84). Pi + SOj-^-P^xo
phosphoric
2H,0,-»-2H 2 0-f O s oxide
 NEW CERTIFICATE CHEMISTRY ACTION OF OXYGEN 277

and was because of these that Lavoisier gave the gas the
Deflagrating
P4 + 30„->-P 4 0„
it

name oxygen (acid-producer).

phosphorous
'spoon
oxide

On solution in water: Action of oxygen with metals to form bases

6H 2 O + P«O 10 -h-* 4H P0 Magnesium. Lower a piece of burning magnesium ribbon by means

3 4
burns with a more dazzling
phosphoric of tongs into a gas-jar of oxygen. It
flame and forms a white ash, magnesium
acid oxide.
Oxygtn
6H,0 + P 0, 4 > 4H 3 PO a 2Mg + 2 -»-2MgO2+
phosphorous
acid or 2Mg + 0,->2(Mg 0*-)
oxidising agent by
Sulphur. In a similar manner, lower a Here, and in similar cases, oxygen is acting as an
accepting electrons (from the metal).
piece of burning sulphur into a gas-jar
Iron. Attach a piece of iron wire to the end
of a deflagrating spoon
of oxygen containing blue litmus solu-
and dip the end of the wire in sulphur (to start the action).
Warm the
tion. Misty fumes of sulphur dioxide
wire in the Bunsen flame until the sulphur begins to burn and then
are given off as the sulphur burns more
plunge it quickly into a gas-jar of oxygen which contains a little
brightly with its characteristic blue flame,
water. The iron wire burns, giving off a shower of sparks, and finally
and this gas dissolves in the water to
form sulphurous acid, which turns the a molten bead of oxide drops into the water.
litmus red. 3Fe +-20 2 -*-Fe 3 4
Fig. 85. tri-iron
Phosphorus burning in S +O — g
»• SO* tetroxide
oxygen. sulphur oxygen sulphur
dioxide
Industrial preparation
SOs + HjO-i-HjSOa natural for
sulphurous Since oxygen exists to such a large extent in air, it is
source. not easy to do
acid attempts to be made to obtain it from this It is

element and cannot readily combine

Carbon. Perform the same experiment with wood charcoal (car- this, since nitrogen is an inert

with anything and thus leave the oxygen pure. By far the best pro-
bon). The charcoal burns and emits a shower of sparks, combining
cess for obtaining oxygen industrially is from liquid air.
vigorously with the oxygen to form a colourless gas, carbon dioxide
Liquid air. Air is first compressed to about 200
atmospheres pres-
which dissolves in the water to form carbonic acid. This is only a
sure, cooled and allowed to escape from a small jet. Expansion cools
very weak acid and the litmus is turned claret-coloured but not
further because heat energy is used in separating the molecules.
definitely red. the air
The cooled air is allowed to flow away by passing round tubes con-
CM-O t -*-COj taining the incoming compressed air. This cools the
incoming air
carbon dioxide
finally sufficient to liquefy the
and these successive coolings are
COa+HjO-^HjCOg air. On evaporation of the liquid,
nitrogen (b.p. 77 K) is first evolved,
carbonic acM K
at 760 mm). This is
leaving a liquid very rich in oxygen (b.p. 90
If the above experiment performed with lime-water in the place of liquid Oxygen is sold for com-
is
a fractional distillation of the air.
litmus solution, the lime-water will become turbid because of the mercial use, not as liquid, but as gas compressed in strong steel
formation of a precipitate of chalk. cylinders at about 100 atmospheres pressure.
Ca(OH),-f CO, * CaC0 + H,0 3
lime-water chalk Uses
(calcium (calcium
(1) As anaid to breathing where the natural supply of oxygen is
hydroxide) carbonate)
insufficient, for example, in high-altitude flying or climbing, and
also
The above oxides are examples of anhydrides (that is, are administered to a patient.
when anesthetics
oxides of non-metals which react with water to form acids),
278 A NEW CERTIFICATE CHEMISTRY QUESTIONS 279

(2) In the oxyacetylenc flame, which can be used for welding and The salts from the acidic reactions are sodium zincate and sodium
for cutting even very thick steel plate. The temperature of the flame aluminate.
reaches about 2200°C. neutral oxide is an oxide which shows neither basic nor acidic
A
(3) In the new L-D process for making steel (p. 486) A great and character (as defined above), e.g., dinitrogen oxide, carbon mon-
increasing oxygen tonnage is now used in this way. oxide.

The oxygen molecule QUESTIONS

It is known directly by experiment (p. 115) that 2 volumes of hydrogen 1. Under what conditions does oxygen react
with the following sub-
combine with 1 volume of oxygen to form 2 volumes of steam (in constant stances: (a) phosphorus; (b) sulphur; (c) magnesium; (d) copper?
Name
classify them.
conditions which do not condense the steam). Applying Avogadro's Law the products and mention any manner in which you could
to the oxygen and steam, 1 molecule of oxygen yields 2 molecules of would you employ pure nitrogen monoxide (contained in a
2. How
steam. Since the minimum quantity of oxygen possible in 1 molecule of vessel under pressure) to estimate the volume of oxygen in a sample of air
steam is 1 atom (atoms being indivisible for chemical purposes), 1 enclosed over water in a graduated tube?
molecule of oxygen must supply at least 2 atoms of oxygen and is,
3. Describe the preparation and properties
of oxygen. If you had two
therefore, at least a diatomic molecule. As additional evidence, no case
vessels, one containing air and the other oxygen,
how would you dis-
is known in which 1 volume of oxygen produces more than 2 volumes
tinguish them by simple tests? (O. and C.)
of a gaseous compound in constant conditions. This points to an actually
diatomic molecule, O t , for oxygen. 4. Describe an accurate method of finding the percentage of oxygen in
Further, the ratio of the two specific heats of gaseous oxygen is (by I (i,» Air

experiment) 1.40, specific heat at constant pressure being greater than How do you account for the percentage being so nearly constant when
specific heat at constant volume. This is the recognised ratio for a diatomic there are causes which remove oxygen from the air? (L.)
many
gas and confirms the diatomicity of the oxygen molecule. 5. Manganese dioxide is said to catalyse the
decomposition of potassiuni
chlorate; what does this statement mean ? Describe experiments you
would
carry out to prove that the statement is true. (O. and C.)
Classification of oxides
6. Describe one method for the quantitative
estimation of oxygen in the
Four important types of oxide are the following. air. State the precautions which are necessary to obtain
an accurate result.
A basic oxide a metallic oxide which reacts with an acid to
is Calculate the density of air (in terms of hydrogen) on the assumption that
air is a mixture of four volumes of nitrogen and one volume of
oxygen.
produce a salt and water only; if soluble in water, it forms an alkaline
solution, e.g.,
(H = 1; N- 14; O- 16.) (N.U.J.B.)
Outline the usual laboratory preparation of oxygen. How is it
7.
CaO + 2HC1 -»• CaCl a + H sO; CaO 4- H,0 -> (Ca(OH), collected ? (Details of apparatus are not required.) How is oxygen
obtained
(alkali) from the air?
Other examples are: Na 80, K 2
(alkalis NaOH, KOH); CuO, Describe an accurate method for measuring the percentage by volume ot
MgO. oxygen in the air. (Methods involving the use of a bell-jar should not be
An acidic oxide is a non-metallic oxide which, when combined how oxygen may be converted into ozone. (N.U.J.B.)
State briefly
with the elements of water, produces an acid, e.g., perform in the laboratory,
8. Describe two experiments which you could
one in which oxygen justifies its name of acid-producer and one
which
SO, + H.O ->- H 2SO«; P<0,o + 2H -> 4HPO s
2
the
gives an opposite result. What evidence is there that the gases of
Other examples are C0 2 SO,, SiO g (acids, H CO a H S0 H Si0 3 ).
,
2 , 2 3, 2
atmosphere are not chemically combined with each other?
An amphoteric oxide is a metallic oxide which can show both basic
9. Describe the usual preparation and
collection of oxygen in the
and acidic properties, i.e., can react with both acid and alkali to
laboratory. State how oxygen may be converted into (a) an acidic
oxide;
produce a salt and water only. (b) an alkaline oxide; (c) an insoluble basic
oxide; (d) an allotropic form.
Examples are ZnO and A1 2 3 . Give also a sketch illustrating (</). (L.)

Basic + H 2 SO« -»- ZnS0 4 + H

ZnO
+ 6HC1 2A1C1„ + 3H 2
Al a 8
- 2

Acidic ZnO + 2NaOH + H -* Na,Zn(OH) 2 4

AJ.O, + 2NaOH + 3H sO -»• 2NaAl(OH)«
 HYDROGEN PEROXIDE 281

Note. If the solution is acidic it will contain some barium ions but
thesedo not interfere with the tests.

Properties of hydrogen peroxide

The pure compound is a syrupy liquid. It is usually used in dilute

Chapter 21 solution in water.

Action of heat on hydrogen peroxide

Hydrogen Peroxide and Ozone Warm hydrogen peroxide solution in a test-tube. Effervescence
occurs. Thegas given off is oxygen. The gas will not rekindle a glow-
ing splint because of the presence of steam.

HYDROGEN PEROXIDE 2H 2 2 -*2H 2 + 2

It willbe readily understood from the above action that hydrogen

water, H 0.
THE commoner oxide of hydrogen
addition, another oxide, hydrogen peroxide, H
forms, in
This com-
is 2

2 2.
It
peroxide acts as an oxidising agent.

pound is a colourless liquid and has been known for more than a Action of hydrogen peroxide on lead(II) sulphide
century. Its purification is difficult and it was not until 1894 that it
Precipitate lead(II) sulphide by passing hydrogen sulphide into a
was obtained in a pure state.
solution of lead(II) nitrate in a boiling-tube. Allow the precipitate to
settle, pour off the liquid and add to the black lead(U) sulphide some
Preparation of hydrogen peroxide, HO 2 g hydrogen peroxide solution. Leave it to stand for some time, shaking
Hydrogen peroxide may be prepared by acting upon the peroxides occasionally. The precipitate gradually turns white, because it is

of certain metals with acids. The materials usually used are barium slowly converted to lead(II) sulphate.
peroxide and dilute sulphuric acid, because the barium sulphate PbS + 4H.O, -> PbS0 4 + 4H tO
produced is insoluble and can be filtered off.
Hydrogen peroxide is here acting as an oxidising agent, oxidising
BaO s + H S0 -* BaS0
2 4 4 j + H2 2
lead(II) sulphide to lead(II) sulphate, and being itself reduced to

To 200 cm of water add 20 cm3 of concentrated sulphuric acid.

3 water.
Place the beaker containing the dilute acid in a freezing-mixture of This reaction is used in restoring pictures. Hydrogen sulphide in
ice and salt and allow it to cool. Gradually add to it a quantity of the air reacts with the white lead paint (lead(II) carbonate) of the
previously moistened hydratcd barium peroxide until the mixture picture to produce lead(II) sulphide, which is brown and makes the
only just reacts acid. Then allow the mixture to settle and filter it. picture dingy. Washing with hydrogen peroxide restores the white
Add to the filtrate a few drops of baryta water (barium hydroxide colour.
solution) until it is accurately neutral, and the resulting aqueous
solution of hydrogen peroxide is ready for use. Action of hydrogen peroxide on acidified potassium iodide solution
The above method of making hydrogen peroxide gives a pure Acidify a solution of potassium iodide with dilute sulphuric acid.
solution, but the yield is small unless great care is taken with the Add hydrogen peroxide. A brown coloration is caused by the pro-
experiment. duction of free iodine.
For the reactions of hydrogen peroxide make a solution as follows: 2KI + H S0 4 + H -» K 2 S0 4 + I, + 2H,0
2 2 2
Dilute about 5 cm of syrupy phosphoric acid with its own volume
3

Here again, hydrogen peroxide is an oxidising agent, oxidising

of water. Cool under the tap and add in small portions at a time two
potassium iodide to iodine, and being reduced to water.
or three saltspoonfuls of barium peroxide. Filter the solution and
In ionic terms, this equation is:
use it for the reactions described below.

3BaO., + 2H 3 PO« -* Ba 3 (P0 4 ) 2 | + 3H 2 2

21- + 2H+ + H,O s
-»- 2H,0 + I,

280
282 A NEW CBRTIFICATB CHEMISTRY OZONE 283

The iodine ion is oxidised by electron loss, as: 2I - — 2e~—y I,. The (Ag+ ) a Oa ~ + 2H+ + 2e~ -> 2Aga++ H O a

electrons are accepted by the oxidising agent, as: MnO«~ + 8H+ + 5e~ -»- Mn + 4H a

2H+ + H O a + 2c--> 2H,0

a
PbO a + 2H + + 2e~ -> PbO + H aO
That is, hydrogen peroxide is reduced by electron gain. Hydrogen peroxide is decomposed cataly tically by many substances,
e.g., manganese
dioxide, finely powdered gold and platinum.
Hydrogen peroxide also oxidises an iron(Il) salt, e.g., FeS0 4, in
acidic solution to the iron(III) state, the solution turning from green 2H a O a ^-2H O a +O a

Add a pinch of manganese dioxide to about 5 cm of hydrogen

3
to yellow.
2Fe* + + H O + 2H" -> 2Fe» + + 2H O
a a a peroxide solution in a test-tube. Oxygen is rapidly
evolved.

A solution of a soluble sulphite is similarly oxidised to sulphate.

Sale of hydrogen peroxide
scy- + H aO a
-*- so 4«- +HO t
Hydrogen peroxide is sold retail in *10 volume* and '20 volume'

of the solution yields 10 cm or 20 cm of

powerful oxidising action makes hydrogen peroxide useful as a
Its 3 3
solutions, i.e., 1 cm3
bleaching agent. It oxidises many dyes to colourless substances, decom-
oxygen at s.t.p. when heated. To minimise loss by catalytic
without damaging the fabric carrying the dye. It bleaches hair to the pure possible and the con-
position, the solutions should be as as
well-known 'peroxide blonde' colour, and is also used for bleaching from roughness. Some additives, e.g., acetanilide, can act
tainers free
the more delicate materials, such as silk or feathers. It is also em- purity the best safeguard.
as stabilisers (negative catalysts) but
is
ployed for cleansing wounds.

Hydrogen peroxide in reducing actions OZONE

Action on kad(IV) oxide. Suspend some lead(TV) oxide in dilute electrical
Ozone can be prepared from oxygen by the use of the silent
nitric acid. Add hydrogen peroxide. Effervescence occurs with evolu-
discharge. The apparatus is shown in Fig. 86.
tion of oxygen (rekindles a glowing splint). A colourless solution
Dry oxygen is passed through the space between the glass
tubes.
remains. In this reaction, lead(lV) oxide converted to Iead(II) connected to the
is coated with tin-foil (T), which is
is
Each tube
oxide, PbO, which dissolves in the nitric acid. Hydrogen peroxide is No actual sparking takes place between
terminals of an induction coil.
converted to water. come into contact with
the layers of tin-foil, nor does the oxygen
PbO, +HO a a
-*• PbO + H a O + O a
them, but a state of electrical strain exists. The
issuing gas may con-
PbO -f 2HNO a -»- Pb(N0 3 ) a + H 2 tain up to 5% of ozone. This ozonised oxygen should not be allowed
Similar reactions occur, with evolution of oxygen, when hydrogen to come contact with rubber, which is attacked by ozone.
into
peroxide reacts with silver oxide, acidified potassium permanganate 30 a -* 20 3
solution and ozone. ozonised oxygen.
Other forms of apparatus may be used for making
Ag a O + H aO -v 2Ag a -f- HO+O
a t

Silver oxide is reduced to metallic silver (a black precipitate).

2Mn0 4 - + 5H aO a + 6H+ —> 2Mn 2+ + 8H a O + 50, >. Ozonised
The permanganate ion is reduced to a manganese salt. \0f7fftn

O s + H a O a -> H a 4 20 a
Ozone reduced to oxygen.
is

In these reactions, hydrogen peroxide appears to act as a reducing

f
Calcium
agent by losing electrons (in association with hydrogen ions), as: Chloride.

H O -* 2H+ + O +
a a a 2e~
The electrons are accepted by the other reacting substance, acting as Fig. 86.
an oxidising agent, as: Preparation of ozone.
284 A NEW CERTIFICATE CHEMISTRY QUESTIONS 285

Their principle is the same as above, but dilute sulphuric acid takes
AHotropy of oxygen
the place of the layers of tin-foil.
Oxygen and ozone are allot ropes (p. 287) of the same element; the
Tests for ozone. It possesses a smell which resembles that difference between them is one of
molecular complexity, oxygen
of very dilute chlorine. (It is noticeable near an electrical having a diatomic molecule, 2 and
ozone a triatomic molecule, 3
,
.

fact that each can be con-

machine in operation.) Their chemical identity is shown by the
Ozone oxidises mercury and makes the mercury 'tail', i.e., shown in earlier pages) without change of
verted to the other (as
leave a trail of mercury stuck to glass as the mercury flows weight.
across it. Quite small traces of ozone can be detected in this The following table compares the two allotropes.
way.
Oxygen, O, Ozone, O,

Properties of ozone, 3 Gas at s.tp.

Gas at s.t.p.
Ozone a gas at ordinary temperature and pressure. It is obtained
is
Density 16 (H = 1).
Density 24 (H = 1).

pure by liquefaction and is then a dark blue, explosive liquid, boiling Insoluble in turpentine. Absorbed by turpentine.
at about —
1 12°C under ordinary pressures.
Heat has no action. Heat converts ozone into oxy-
gen. 20 3 -» 30 2 .

Ozone as an oxidising agent No effect on mercury at room Makes mercury 'wet' glass

temperature. ('tailing').
Ozone is a vigorous oxidiser. It oxidises lead sulphide to lead
Attacks rubber.
sulphate No effect on rubber.
Has no effect on potassium iodide Liberates iodine from potas-
PbS + 40 3
-»• PbS0 4 + 40, solution. sium iodide solution.
black while (Equation opposite)
lead(II) lead(II)
sulphide sulphate Oxidising agent. Vigorous oxidising agent.
and hydrogen sulphide to sulphuric acid.

H 2 S + 40 3 -»-H S0 4 + 2 40,
It also liberates iodine from potassium iodide in acidic solution
QUESTIONS
2KI + H S0 4 + O s -»-
2
?
+ 2 + K S0t 4
-4- H2
(iodine 1 How is ozonised oxygen prepared in the laboratory? Describe thrbb
brown experiments to show how it diners from oxygen. If 100 cm" of pure ozone
were heated and then reduced to the original temperature and
coloration) pressure,
This reaction isexpressed in ionic terms as: what would be the volume of the resulting gas? (N.U.J.B.)
peroxide?
2H + + -* I, +O 2 How would you prepare a dilute solution of hydrogen
21- a + 2 +H 2
What is the action of hydrogen peroxide solution on (a) ozone; (/>) lead
The iodide ion is oxidised by electron loss: 2I _ — 2e~ —* I2 ; the sulphide; (c) acidified potassium iodide solution?
electrons are accepted by ozone acting as an oxidising agent: What is meant by a '10 volume' solution of hydrogen peroxide?
(N.U.J.B.)
2H+ + Os + 2e--»- O, + H tO 3. How is ozonised oxygen obtained?
This powerful oxidising action of ozone makes it useful for ventila- In what respects docs this gas differ from
ordinary oxygen? How has
ting places to which fresh air has little access. It attacks the organic it been shown (a) that ozone is
composed of oxygen atoms only ; (6) that
its molecular weight is greater than
that of oxygen? (O. and C.)
compounds which are responsible for the 'stuffy' smell. Some of the peroxide?
London tube railways are ventilated in this way, metallic ozonisers 4 (a) How would you prepare a dilute solution of hydrogen
How does hydrogen peroxide react with (i) ozone; (11) acidified
of the type described above being used to supply ozonised air. The
potassium iodide solution? .„,-»,» j .««
gas becomes poisonous at concentrations exceeding about 1 in 50 000 (b) What volume of oxygen, measured at 136.5 C and 760 mm
of air, by volume. pressure, could be obtained by boiling 100 g of a solution con-
taining 17% by weight of hydrogen peroxide? (N.U.J.B.)
 286 A NEW CERTIFICATE CHEMISTRY
5. Describe the properties of ozone.
On partly ozonising 100 cm 3 of oxygen a decrease of volume of 10 cm'
resulted. What volume of ozone had been produced ? The resulting gas
was treated with excess of a solution of potassium iodide when the follow-
ing reaction took place:

+ 2KI + H.O -> 2KOH + I, + O,

3

Calculate (a) what volume of gas would remain; (b) what weight of iodine
Chapter 22
would be liberated, assuming the volumes to have been measured at
s.t.p. (C.)

6. How can oxygen be converted into its allotropic form? Compare the
properties of oxygen with those of its allotropic form. (O. and C.) Carbon and its Oxides; Flame

CARBON
Occurrence
found in the form of diamond (India, South Africa)
PURE carboncarbon is

and impure as graphite (Ceylon). Carbon a constituent

is

of numerous naturally occurring substances such as coal, mineral oils,

carbonates, organic matter of all kinds and occurs in the air to a small
but very important extent (0.03-0.04% by volume) as carbon dioxide
(see p. 185).

AUotropy of carbon

If an element can exist (without changing its state) in two or more

different forms, the element is said to exhibit allotropy.
The forms of the element are known as allotropes of it. They always
exhibit different physical properties and may have different chemical

properties also.
Carbon exists in the following allotropic modifications:
Diamond. The diamond is in the form of octahedral crystals of
density 3.5 g/cms which have, when cut and polished, an amazing
lustre which makes them valuable as jewellery. It is also the
hardest

substance known and has a commercial value for the manufacture of

glass cutters and rock borers.
Graphite. Graphite exists as black, slippery, hexagonal crystals. It
artificially by
is found naturally as plumbago and is manufactured

heating coke to a very high temperature in the electric furnace

(Acheson process).
It is used extensively in the manufacture of
lead pencils (which
contain a long thin cylinder of graphite and clay) and also as 'black
lead* as a protective coating for iron articles. It is used as a
lubricant,

particularly for small bearings (for example, those in dynamos and

vacuum-cleaner motors) which require little, but regular, lubrication.
287

i
 288 A NEW CERTIFICATE CHEMISTRY CARBON 289
Amorphous carbon (which is really made up of small crystals of
80) These weak forces allow movement
of the planes parallel to each
(o
many forms:
graphite) exists in
other and this makes graphite very soft. The open structure (Fig 87) makes
Animal charcoal \s made by heating animal refuse and bones with a cranhite more liable than diamond to
chemical attack. (See also below.)
limited supply of air. It also contains much calcium phosphate. It In the three-dimensional formation
of diamond, all four valency electrons
has the property of absorbing colouring matter (for example, litmus) oer atom are involved in covalent
bond formation with four adjacent
graphite, only three valency
and has a use in industry in removing the colouring matter from carbon atoms. In the parallel atomic layers of
per atom are definitely located in bond formation, the bonding
electrons
brown sugar. layers being van der Waals forces. Consequently, some electrons
between
Wood charcoal is made by heating wood with a limited supply of mobile and allow it to conduct electricity, which diamond
in graphite are
air. It is a light porous variety, and is a remarkably good does not.
absorbent
for gases (1 cm3 of wood charcoal will absorb nearly 100 cm 3 of
Experimental evidence that graphite and diamond are allotropes of
ammonia gas at 0°C). shown to burn
carbon is the following. Both these substances can be
Lampblack is made by burning oils (for example, turpentine) with of oxygen and the sole product in each case is
when heated in excess
a limited supply of air, and it is used for making printers' ink and the evidence is made quantitative by
carbon dioxide. Further, if
shoe-polish. hydroxide solution or
absorbing the carbon dioxide in potassium
Sugar charcoal is a very pure form of carbon, and is made by weight of carbon dioxide obtained
soda lime, it can be shown that the
removing the elements of water from sugar. same as from one gram of graphite,
from one gram of diamond is the
Coke, gas carbon and soot are other forms of impure amorphous
i.e., 3.67 g.
carbon. diamond with
The following table summarises a comparison ot
Crystal structure graphite.
In diamond, covalency operates between the carbon atoms throughout Diamond
and produces a crystal which is one single molecule which may become Graphite
very large (a macromolecule). The crystal unit contains five atoms, ABCDE 3
3
Density 2.3 g/cm average; vari- Density 3.5 g/cm average; vari-
able able
Colourless, transparent; very
Black, opaque
high refractive index
Very soft, marks paper Hardest known natural sub-
stance
conductor Electrical non-conductor
Good electrical
Not attacked by these reagents
Attacked by potassium chlorate
and nitric acid together

Diamond transparent to X-rays while glass

is is almost opaque. This
test distinguishes the two.

diamond graphite
Properties of carbon
Dots are centres of carbon atoms Carbon is not a very reactive element. All forms of carbon can be
Fig. 87. made to burn in excess of oxygen to form carbon dioxide, although
Crystal structure of diamond and the temperature at which they commence to
burn varies. As the
graphite.
carbon burns a great amount of heat is liberated.
(Fig. 87),and it is repeated indefinitely, forming interlacing hexagons. The
strength and uniformity of bonding make diamond very hard, non-volatile c + o 8 ->co.
and resistant to melting and to chemical attack. In graphite, carbon atoms Sulphur will also combine with carbon at a high temperature to
arc combined by covalency in hexagons in parallel planes. Between
the
planes, bonds are much weaker and are the result of vander form carbon disulphide.
Waals forces
C + 2S-»-CS 2
290 A NEW CERTIFICATE CHEMISTRY CARBON 291

Owing to the fact that carbon combines readily with oxygen, it acts where coal-tar separates as a lower layer with gas-liquor as an aqueous
as a reducing agent and is used in industrial practice in obtaining iron layer above it.
and zinc from their ores. (See p. 483, and p. 481.) The gas then enters scrubbers, where it encounters a spray of water.
This dissolves out any remaining ammonia and also
Reducing property of carbon. Scrape a small hole in a charcoal acidic gases
block and place in the hole a mixture of lead(II) oxide and anhydrous HCN) ammonium This solution is added
(HjsS, C0 , 2
as their salts.
sodium carbonate. (The carbonate melts and forms a protective coat- to the gas-liquor. The impurity, carbon disulphide, in the coal-gas
ing, preventing the metal from being oxidised.) Turn the luminous
is nowconverted to hydrogen sulphide by passage over nickel
Bunsen flame low, direct a jet of flame by means of a mouth blowpipe (catalyst) at 450°C.
on to the mixture and heat it for a few moments. Allow to cool and, CS 2 + 2H -*-2H 2 S-i-C
2
on ejecting the substance from the hole, you will find a small grey
AH the hydrogen sulphide of the gas is now removed in the purifiers,
globule of metallic lead which can be cut with a knife and which will
mark paper. by passage over hydrated ferric oxide.
PbO-f C->-Pb + CO Fe 2O s 3H t S -»• Fe»S 3 + + 3H 2

2- Fe 2 + 3H S -»• 2FeS +S+ 3H a O

In this reaction, carbon in association with the O
ion of the oxide
3 2

and
makes electrons available and, therefore, acts as a reducing agent, as After use, the material is exposed to air to regenerate the oxide

0«- is used again.

+ C-»-CO + 2e-
2Fei S s + 30 2 ->2Fe 8 3 + 6S
The ion, Pb2+ , of lead(II) oxide reduced by accepting these elec-
is
4FeS + 30 -* 5
2Fe.0 3 + 4S
trons, as:
the sulphur content reaches 55%, the spent oxide is sold as a
Pba+ + 2e~ -* Pb When
source of sulphur dioxide (p. 407).
Carbon is common solvents, a fact which all motor-
insoluble in all
The gasthen scrubbed with petroleum oil to remove benzene,
is
car owners know to cost Petrol consists of hydrocarbons similar
their
toluene and naphthalene, which are recovered by
fractional distilla-
to methane, CH«. In the cylinders these hydrocarbons are oxidised delivered to consumers.
tion, after which it enters a gas-holder and is
by the oxygen of the air. If the supply of air is insufficient a deposit
The white-hot coke remaining in the lowest third of the retort has
of carbon is left inside the cylinders as a hard black solid. This would, mixes with
steam passed through it. This produces water-gas, which
in time, choke up the engine and hence the carbon has to be removed.
the coal-gas and improves its thermal quality.
Since carbon is not soluble in any common solvent, this has to be
done by dismantling the engine and removing the carbon mechanic- C + H,0-»-CO + H,
cyanide
Sulphur (in spent oxide) is a by-product and hydrogen
is
ally.

recovered as sodium ferrocyanide.

Coal-gas
Coal is an impure form of carbon and, as such, is used as a domestic To summarise:
Coal
source of heat. Its use is, however, uneconomic, as a considerable
distilled at about I000°C
amount of the heat of the combustion goes up the chimney and also
many valuable products are lost. Further, much of the carbon escapes
as soot, polluting the air in the larger industrial areas.
Coal-gas Gas-liquor Coal-tar Coke
The essentials of coal-gas manufacture in its 'classical' form (i.e.,
until recent changes have modified it) are the following. non- A contains ! is distilled with | is distilled for is used as a fuel,
and as a source of
caking, bituminous coal, finely powdered, is fed continuously down hydrogen, 50%, lime. Ammonia is benzene, phenol,
evolved and ab- toluene, cresol, water-gas and
vertical fireclay retorts heated to about 1000°C by producer gas. The methane, 30%, |

producer gas, and

\

carbon monoxide,
'

sorbed by dil. |
pilch.
volatile products pass by the ascension pipe to the hydraulic main, as a large-scale
8% and small H.SO, to yield
where coal-tar and an aqueous liquor begin to condense. ammonium sul- reducing agent.
amounts of
The gas passes to water-cooled condensers, where more tar and ethylene, CO t '

phate (fertiliser).

aqueous liquor separate out. All these liquids are fed to the tar-well, and other gases.
 292 A NEW CERTIFICATE CHEMISTRY PRODUCER GAS AND WATER-GAS 293

Petroleum is now being applied to the production of a fuel gas to

replace or supplement coal-gas. PRODUCER GAS AND WATER-GAS
Producer gas
Fuel gas from petroleum
Producer gas is a fuel gas made by passing air through a thick layer
Naphtha (p. 324) is vaporised and purified from sulphur com- lower part of the
of white-hot coke in a producer (Fig. 88). In the
pounds which would poison the catalyst in the main reaction. The
producer, with air in excess, the reaction is:
naphtha vapour and steam are passed, in two stages, at 750°C
purified
and 690°C, and at 28 atm. pressure, over a nickel catalyst. Taking C -f 2
—> C0 2 (strongly exothermic; i.e., heat liberated)

C 5 H 12 as typical of naphtha, the reactions can be As the carbon dioxide rises through the mass of white-hot coke, the
summarised as
below. further reaction is:

C 6 H It + 5H 2 0-»- 5CO + HH a CO, -f C -> 2CO (endothermic; heat absorbed)

CO + 3H„ ^ CH« + H s O
CO + H t O^ CO a + H,
The product is passed over heated iron oxide (catalyst) to reduce the
carbon monoxide content. After cooling, some carbon dioxide is re-
moved (by water under pressure or alkali) and the gas is dried. It has
the approximate volume composition carbon monoxide, 3
:
% methane,;
producer
CH 4 34%; hydrogen, 48%; carbon dioxide, 15%. Because of the low
,
gas
carbon monoxide content, this gas is much less poisonous than coal-
gas, and it satisfies British standards of calorific value. A plant using
this process is said toneed only one-eighth of the space and one-sixth coke
of the capital cost of a corresponding coal-gas plant.
Sheet iron with
Recent borings in the North Sea have revealed reserves of natural
gas (mainly methane) estimated (May 1969) to yield 3000 million fire-brick lining
cubic feet of gas per day for. perhaps, 35 years. This daily output
would meet the whole of Britain's current needs of gaseous fuel. Pipe-
lines will have to be laid and appliances modified to correspond with
the fact that natural gas has twice the calorific power of present gas Fig. 88.
supplies (volume for volume). Methane is also being imported, in Manufacture of producer gas.

refrigerated tankers as liquid, from the Saharan oil-fields.

On the balance of these reactions, net heat is liberated and the reaction
Smokeless fuels
can continue indefinitely.
The objections (p. 290) to the burning of 'raw* coal have led to the The gas emerging from the producer consists of carbon monoxide
investigation of smokeless fuels. Coal-gas is, of course, smokeless and (one-third by volume) and unchanged nitrogen of the air (two-thirds).
This producer gas is usually distributed, while still hot from
so is coke. But coke is hard to ignite and burns badly in the ordinary the pro-
domestic grate. ducer, to points on the site where heating is required; it is mixed with
Low-temperature carbonisation of coal has been tried. Coal is dis- secondary air and burnt to produce more heat.
tilled in retorts as in making coal-gas, but the temperature
of distilla-
tion is much reduced (under 750°C instead of about 1000°C). Some
2CO + Ot — 2COj, (exothermic; heat liberated)

coal-gas, oil and tar are produced. The solid residue is a fuel which
Since two-thirds (by volume) of the gas is non-combustible nitrogen,
its calorific value is not high and the gas is
not distributed to con-
ignites and burns much more readily than coke and is smokeless.
So
far, however, this solid fuel is too expensive compared with
sumers as town-gas is. It has been found very useful, however, in such
'raw' and glass furnaces.
processes as the firing of retorts
coal.
 CARBON DIOXIDE 295
294 A NBW CERTIFICATE CHEMISTRY
Water-gas Preparation or carbon dioxide
Water-gas is produced by the passage of steam through usually made in the laboratory by the action of dilute hydro-
It is
a mass of
coke at a temperature (minimum 1000°C) which allows chloric acid on marble.
the reaction: bottle), as shown in
Place several pieces of marble in a flask (or
C -f H,0 —* CO + H, (endothermic; heat absorbed) hydrochloric acid down the thistle
Fig 89, and pour some dilute
giving equal volumes of carbon monoxide and marble. There effervescence and a colourless gas
hydrogen, both of funnel on to the is

which are combustible, so the gas has a high calorific value. collected over water or by downward delivery,
1
is liberated which is
As shown, the above reaction is endothermic, so the temperature the gas being denser than air.
Calcium chloride solution is left in the
of the coke falls. Below 1000°C, much steam passes
without reaction flask.
and, also, incombustible carbon dioxide is formed.
CaC0 3(c) + 2HCl(aq) ->- CaCl s (aq)+ H sO + C0 2 (g)

C + 2H 2 0-»-CO, + 2H 2
or CO/" 2H- -I-
—H 2 + C0 2

To meet this situation, the plant similar to the pure and dry it can be passed through potas-
If the gas is required
producer above, is remove sus-
used in the following way. An air-blow of about two minutes sium hydrogen carbonate solution in a wash-bottle (to
raises it through a calcium
the temperature of the coke to incandescence (perhaps 1400°- pended hydrochloric acid), dried by passing

1500°C), using the exothermic reaction of producer gas (above). chlorideU-tube and collected by downward delivery (the gas being
Then
a steam-blow of about four minutes produces water-gas, which denser than air).
is
collected. This cools the coke and the air-blow is renewed and
so on
alternately. Dilute Hydrochloric
Acid
Water-gas can be burnt as a fuel gas with air, both the following Carbon
reactions being exothermic. O/oxide

2H, + Oa - 2H O; 2CO +
s 2
-* 2CO a

Water-gas has been an added constituent of town-gas for many years,

being made by the action of steam on the white-hot coke residue in
the retorts. The high carbon monoxide content makes the gas more
poisonous. It has also been an industrial source of hydrogen and of
organic chemicals, e.g., to make methanol. Water-gas and hydrogen
are passed, with heating to 450°C, over a catalyst (oxides of zinc and f/ar6le^^m^=,
chromium) at 200 atm pressure. Fig. 89.
Preparation of carbon dioxide.
CO + H + H, -»- CH,OH
2

water-gas and perform the following experi-

Collect several gas-jars of the gas,
ments:

CARBON DIOXIDE Effectof carbon dioxide on a lighted splint. Plunge a

lighted

splint intoa gas-jar of the gas. It is extinguished. Carbon

This gas was first observed by Van Helmont towards
the end of the
dioxide docs not support combustion.
sixteenth century, but Black (1728-99) showed that the gas could
first
Action of carbon dioxide on lime-water. Pour lime-water
be prepared by the action of dilute acids on calcium carbonate. It
into a gas-jar full of carbon dioxide. The lime-water goes
occurs in the air on the earth's surface to the extent of about 0.03%
milky. the mixture is allowed to stand, you will see white
If
of its volume; it issues from rocks in volcanic regions, and occurs in particles of chalk.
solid particles separate out. These are
mines as 'choke damp'. Certain mineral springs contain the gas and
it is always present in natural drinking water because of its solubility » There is some loss due to the solubility of the gas in water. Water, at ordinary
temperature and pressure, absorbs its own volume of carbon dioxide.
in water. Its biological importance is dealt with on p. 185.
296 A NEW CERTIFICATE CHEMISTRY CARBON TETRACHLORIDE 297

The milkiness is due to a suspension of the insoluble sub- soluble. Put a glass plate over the
mouth of the jar and remove it.
stance, chalk, in water. litmus solution and shake. The solution
To the liquid in it, add blue
not This is because carbon dioxide
Ca(OH), + CO -> CaCO
s a H 2
becomes claret-coloured but red.
which however, too
calcium carbon calcium water reacts with water to produce carbonic acid, is,

hydroxide dioxide carbonate

weak to turn litmus solution red.
solution (chalk)
(lime-water) HoO + CO, ^ H sCO s ^ 2H+ + CCV"
(very slight)
watcr carbon carbonic
The above test serves to distinguish carbon dioxide from acid
dioxide
any other gas.
Carbon dioxide is an acidic oxide.
Effect of carbon dioxide on a lighted candle
hydroxide solution
Lower a candle on a deflagrating spoon into a gas-jar of air. The Action of carbon dioxide with sodium
solution
candle can be extinguished by 'pouring' carbon dioxide into the gas- Repeat the above experiment, using sodium hydroxide
jar in which the candle is burning (Fig. 90). This shows carbon water. The rapid rise of the solution shows that the gas is
instead of
reacts with the alkaline
dioxide to be denser than air (density 22 relative to hydrogen). quickly absorbed. The acidic carbon dioxide
solution producing sodium carbonate.
CO + 2NaOH -* Na 2C0 3 + H,0
g

or CO* + 20H- -* C0 3*- + H 2

This reaction is discussed more fully later (p. 312).

Uses of carbon dioxide

(the taste of soda
Solutions of the gas in water have a pleasant taste
effervescing
water), and hence the gas is used in the manufacture of the
caused by dis-
drinks' called 'mineral waters*. The
effervescence is

a pressure of several atmospheres; when

solving the gas in water at
(by opening the bottle) the gas is liberated.
the pressure is released
Its use in the solid form is increasing.
Carbon dioxide can be made
into a white solid (carbon dioxide snow) by allowing liquid carbon
dioxide to evaporate, the temperature falling to -78°C as the solid
This solid evaporates when heated, leaving no residue, and it
Fig. 90. forms.
Pouring carbon dioxide on to a candle. is, therefore, used as a refrigerating agent for perishable goods.
non-inflammable nature, carbon dioxide is used for
Owing to its
Effect of burning magnesium on carbon dioxide extinguishing fires. extinguisher contains a solution of
The usual fire
contact with
Lower a magnesium into carbon dioxide in a
piece of burning sodium carbonate which can be made to come into
The carbon dioxide liberated
gas-jar. It continues to
burn for a short time with a spluttering flame, dilute sulphuric acid by striking a knob.
effervescing liquid on to the fire, and the carbon
and black specks of carbon can be seen on the sides of the gas-jar. forces a stream of
prevents the air from getting to the burning material and so
The- magnesium burns to magnesium oxide dioxide
helps to put out the fire. For solid CO, crystals, see p.
73.
2Mg + CO -*-2MgO-r-C
i

This clearly shows carbon dioxide to contain carbon and oxygen. CCI 4 tetrachloromethane
Carbon tetrachloride, ,

Solution of the gas in water This compound is made by chlorinating carbon disulphide, boiling
under reflux, with iodine as catalyst.
Invert a gas-jar of carbon dioxide in a trough of cold water and
shake the gas-jar. The water rises slowly, showing that the gas is cs, + 3a,->cci4+s^a,
 298 A NEW CERTIFICATE CHEMISTRY CARBON MONOXIDE 299

The products can be separated by fractional the partial combustion of carbon, and poisoning by the exhaust
for example a garage, is
distillation (boiling-points, CCI
4 77°C, S 2 CI 2 fumes of a motor-car in an enclosed space,
138°C at standard pressure). The carbon tetra- due to the presence of carbon monoxide. The blood of a person
characteristic cherry-red in colour. An atmos-
chloride can be purified by shaking with dilute poisoned by the gas is a
sodium hydroxide solution (to remove any phere containing as little as 0.5% carbon monoxide may cause death
and an atmosphere containing 0.1 / is
chlorine) and then with water. This is done in a if breathed for some time,
separating funnel (Fig. 91). Carbon tetrachloride injurious.
is almost non-miscible with water and separates
Preparation from oxalic acid
as the lower layer (density, 1.63 gem"3) which
is run off through the tap. The washing liquid Fit up the apparatus as shown in Fig. 88. Place some oxalic acid
crystals (H i C lO«.2H,0) in the strong
flat-bottomed flask and pour
(upper layer) is poured out through the top of the
concentrated sulphuric acid down the thistle funnel.
Warm the mix-
funnel. Anhydrous calcium chloride (bean size)
ture gently (always have the greatest
respect for hot concentrated
is then added to the carbon tetrachloride and the
effervescence is observed,
mixture is left in a stoppered flask for at least 12 sulphuric acid). The white crystals dissolve,
and a mixture of carbon monoxide and carbon dioxide gases is
hours. This will dry the carbon tetrachloride as
By passing the mixture through a concentrated solution of
the calcium chloride takes up the water present evolved.
the carbon mon-
caustic potash the carbon dioxide is absorbed, and
as the solid hydrate, CaCI a .6H 2 0. The liquid water which it is insoluble.
should then be decanted (or filtered through a oxide passes on and is collected over in

dry filter-paper) into a dry distillation flask and 2KOH + CO,->- K 2C0 + H aO
3

distilled (apparatus as p. 191). If pure, the entire

C
Chemistry of the action. Oxalic acid has the formula H 2 20«
and
Fio. 91. of water
acid removes the elements
Separating funnel. liquid should distil over at its boiling-point, the hot concentrated sulphuric
equal volumes
77°C, at standard pressure. from the molecule of oxalic acid, leaving a mixture of
Properties and uses oxalic acid crystals

1. Carbon tetrachloride is a good solvent for fats and grease and and concentrated
isused as a de-greasing and dry-cleaning agent. I sulphuric acid
It has the advantage
of being non-inflammable. Cone, potassium
2. As pyrene, it is used as a fire extinguisher over small areas, e.g., hydroxide soln.

a motor-car engine. Its vapour is very dense (about 5.5 times as dense to absorb carbonyl carbon
as air) and tends to blanket the fire and extinguish it by excluding air. dioxide .
'monoxide
A disadvantage is that air at a very hot surface can oxidise it to
carbonyl chloride, COCI 2 , a very poisonous compound. Water
3. By heating with iron and water, carbon tetrachloride is con-
verted to chloroform.
CC1 4 + Fe + H + -> Fe 2+ + CI" + CHC1 3 Fio. 92.
Otherwise, it ischemically rather inert; unlike most non-metallic
Preparation of carbon monoxide.
chlorides, it is unaffected by water.
dioxide. It is because the carbon
The carbon shaped like the methane
tetrachloride molecule is of carbon monoxide and carbon
molecule (p. 75), substituting four chlorine atoms for the four quantity, and not merely as a small trace of im-
dioxide is there in
hydrogen atoms of methane. is necessary to pass the
gas through two wash-bottles
purity, that it

containing potassium hydroxide solution.

CARBON MONOXIDE H Cs
2 4 -H 2
0-»-CO + C0 2
carbon carbon
oxalic water
Carbon monoxide a poisonous, colourless gas with practically no
is
(removed monoxide dioxide
acid
smell. It is present in coal-gas and other gaseous fuels. It is formed by by acid)
 300 A NEW CERTIFICATE CHEMISTRY CARBON MONOXIDE 301

Preparation from formic acid Reducing properties of carbon monoxide

Fit up the apparatus shown in Fig. 93. Place one or two teaspoonfuls Take a hard-glass tube containing a porcelain boat full of lead(H)
of sodium formate in the fiat-bottomed flask and allow concentrated After allowing
oxide and pass carbon monoxide through it (Fig. 94).
sulphuric acid to run in from the tap funnel. The reaction takes place moments for the hard-glass tube to be filled with the gas, light
a few
the jet and heat the lead(II) oxide. A
in the cold, effervescence is observed and carbon monoxide
is col-
glow will spread through the
lected over water in which it is insoluble. lead(Il) oxide and, on allowing the apparatus to cool, grey metallic
observed. The carbon monoxide has reduced the lead(II)
lead will be
Cone oxide to lead, being itself oxidised to carbon dioxide.
Sulphuric
acid PbO(c) + CO(g) -»- Pb(c) + CO,(g)
Carbon
Monoxide The gas will similarly reduce copper(II) oxide and iron(IH) oxide
to the metal.

Water CuO + CO ->- Cu + COj

Sodium
Formate Fe 2O s + 3CO -> 2Fe + 3CO,
all these reactions, carbon monoxide, in
association with the
In
as a
s-
ion of the oxides, makes electrons available and so acts
Fig. 93. reducing agent, as:
Preparation of carbon monoxide. O*- CO -»- + 2 2e~ C0 +
The metallic ion is reduced by accepting these electrons:
Chemistry of the action. Sodium formate is converted into formic
acid from which the elements of water are immediately removed
Cu* + +
2e~ ->- Cu

the concentrated sulphuric acid

by Pb ,+ + 2e~ -* Pb
2Fe 3+ + 6e~ -»- 2Fe
HCOONa + H 2 S0 4 -»- HCOOH + NaHS0 4
HCOOH-H a O->-CO carbon monoxide burning
removed
by acid to carbon dioxide
The above actions take place simultaneously and can be represented lead (n)
by the equation carbon oxide
monoxide
HCOONa + H,S0 4 ->• NaHS0 4 + CO + H sO
Test. Carbon monoxide burns in air with a
blue flame,
forming carbon dioxide (the latter will turn lime-water
turbid, forming a precipitate of chalk).

Collect a gas-jar of the gas and perform the following

experiment:
Action of lime-water. Take away the glass plate,
quickly pour in a
little lime-water and shake. There
should be no turbidity. (It may be
very difficult to get rid of all the carbon dioxide Fig. 94.
present. If necessary,
shake first with potassium hydroxide solution.) Apply Reduction oflead(II) oxide by carbon monoxide.
a light to the
gas and it will burn with a blue flame, and on
shaking, the lime-water
will go turbid.
Preparation of carbon monoxide from carbon dioxide
2CO + O - •2C0 2
Carbon monoxide may be prepared by passing a stream of carbon
t
carbon oxygen carbon
heated to
monoxide (air) dioxide dioxide through an iron tube packed with pieces of carbon
 302 A NEW CERTIFICATE CHEMISTRY FLAME 303

carbon
FLAME
Definition. Flame is a region of combining gases which radiate light
GAS HEATED
and heat.
FURNACE Examples of flame with which you are familiar are the burning in
coal-gas, wood or coal. In the
air of such materials as hydrogen,
last case, wood or coal when heated give out gases which will burn

in air and since the wood or coal

are supplying these combustible
potassium gases, the flame is closely associated with the solid matter. In every
hydroxide flame, there produced by the chemical reaction so much heat that
is

solution the system is We know, on the other hand,

raised to incandescence.
many cases where gases combine slowly with little rise of tem-
Fio. 95.
perature and no flame. An example of this type of reaction is the
Preparation of carbon monoxide by passing carbon
hydrogen and chlorine when left in contact with
dioxide over red-hoi carbon. combination of
each other in diffused daylight.
combustion
red heat (Fig. 95). Any carbon dioxide present is then absorbed by The terms 'combustible material' and 'supporter of
caustic potash solution and the gas collected over water. are interchangeable.
Bunsen flame usually refer to the
in air, we
C + C0 2 ->2CO When considering a
from the burner as the 'combustible material' and
the
carbon carbon carbon gas coming
dioxide monoxide air as the 'supporter of combustion'.
This is mainly because we live
(which contains oxygen, a very reactive
in an atmosphere of air
accident, this
Reactions in a domestic fire gas) which surrounds any burning material. If, by
would be possible
The reactions in a deep, brightly glowing coke or coal fire are atmosphere of ours were to consist of coal-gas, it

to produce the flame of a Bunsen burner by

similar to that by which carbon monoxide is produced in the
last
experiment. They are sufficiently explained in Fig. 96. pumping air down the pipe usually connected
to the gas-works. To illustrate this, set up the
apparatus shown in Fig. 97, which consists of
asbestos
a lamp chimney with a square of
(containing a round hole) resting on the top

of the chimney. The cork at the base is

fitted
At A plenty of air available. Carbon
burns to carbon dioxide. with a glass tube for a gas inlet and a mica or
C + O, -»• CO, metal tube at B. The gas is turned on, and the
At B ascending carbon dioxide
aperture at A is closed momentarily whilst the
is
reduced by red-hot carbon to carbon gas issuing from B is ignited. The aperture at
monoxide. A is now opened and the gas is lighted. On
CO, + C -* 2CO inspection, be seen that there is now a
it will
At the surface the hot carbon mon- flame at the top of the mica tube which consists
oxide burns in the air (to form carbon of air burning in an atmosphere of coal-gas.
Bars dioxide) with a flickering blue flame.
i

graU\ \ »— ZfAir 2CO+ 0,->2CO, Structure of flame

Mm The structure of a flame varies according
Fio. 96. to the chemical composition of the gas which Fio. 97.
The household burning. The is brought
general conical shape
fire. is Air burning in
about by several factors, the more important coal-gas.
 304 A NEW CERTIFICATE CHEMISTRY
of which are the effects of convection and the necessity for further
supplies of gas to search for air with which to burn. The gas burning
^ FLAMB 305

immediately on issue from the burner, uses up the air in that region
and the gas following has to seek its supply of air from more distant
sources. At the same time the convection currents set up confine this
search to an upward direction. The blue zone seen at the base of
a
Bunsen or candle flame (see Fig. 99) is caused by the upward stream
of air impinging on the base of the issuing cone of gas. The inner
zone near the burner contains unburnt gas, since the outside of the
flame has obviously the best opportunity to come in contact
with
the air, and the inside of the flame, the least.
We will consider the structure of some well-known flames:
(a) The flame of hydrogen burning This flame is, as we should
in air.
expect, a simple one. Two zones only are produced, a zone
of unburnt
gas surrounded by a zone in which combination of oxygen and hydro-
gen takes place. The flame is almost invisible in dust-free
air (See
Fig. 98).

of comoination
'nburnt yua

A
Luminous coal-gas flame.
Fio. 98. Candle flame.
Hydrogen flame. Fig. 99.

The candle flame. Candle-wax consists of hydrocarbons, both

(b)
the carbon and the hydrogen being combustible materials. It is as-
sumed that both elements do not burn completely to form water and
carbon dioxide except at the very outside of the flame where there
is plenty of air. In the bright yellow zone there is incomplete com-
bustion and particles of carbon raised to a white heat are present
in
it to give the flame most of its luminosity,
whereas the outside zone
where combustion becomes complete is only faintly visible. The zone
round the wick consists of unburnt gas, and the blue zone at the base
is a zone of rapid burning caused by the upward
rush of air (due to
convection) first meeting the combustible gases. (See Fig. 99.) |Stream of gas draws m
J/ "^iair from outside when
The luminous Bunsen flame (air holes closed) gives a parallel with oirWes open
the candle flame, the gases in the coal-gas being methane
(a hydro-
carbon), hydrogen and carbon monoxide.
(c) The Bunsen flame. The flame of a burning hydrocarbon
or the Gas
luminous Bunsen flame is not a very hot flame and deposits soot on a
cold article held in it. Bunsen devised a simple burner (Fig. 100) to
ensure more complete combustion by introducing a supply of air
entering with the gas, so that this supply of air together with the Fio. 100.
Bunsen burner.
 306 A NEW CERTIFICATE CHEMISTRY
external supply is sufficient toproduce complete combustion. Hence
the flame with the air holes open is more compact, much hotter and
non-luminous. The structure of this flame is shown in Fig. 101, and it
willbe seen that the luminous zone has been replaced by a zone in
which the coal-gas burns with the internal supply of air. There is a
limit to the amount of air which can be supplied by the holes at
the
base, for if sufficient is introduced to cause almost complete
com-
bustion, the rate of burning of the mixture exceeds the speed at which
the gas is moving up the tube and the flame 'strikes back*.

Gas burning trffn air

mainly supplied
from outside

Gas burning with air

supplied from base

Unburnt gas

Humphreys and Glasgow Lid.

Plate 5. (a) (Above): Manufacture of

carburcucd water-gas. Producer-gas
and water-gas arc made in turn in the
tapered vessel (/<•//). Oil is introduced
in the two large cylinders to improve
the calorific value of the gas.

Fio. 101.
Non-luminous Hansen flame.

Experiments to illustrate the structure of flame. The existence of a

zone of unburnt gas and zones of varying temperatures may be
shown by exploring the flame in the following way: hold a piece of
paper or cardboard horizontally in the flame and remove it just be-
fore burning would occur (Fig. 102). The inner zone will be found to
cause no burning of the paper, whilst the hot parts of the flame will
turn the paper brown. Alternatively, copper gauze may be held in
the flame by means of tongs.

Plate 5. (b) (/.<//): Ammonia con-

venors in the I.C.I, works at Billingham.

r— Jul f*i<*„.i.„i iii.Unii', i /././.

 FLAME 307

The causes of luminosity of flame

The luminosity of a flame is affected by alteration of temperature
and pressure of the burning gases and also by the presence or absence
of solid particles.

Fio. 102.
Exploring temperature of flame.

Fisam The presence of solid particles in a flame increases luminosity.

Plate 6. Manufacture and use of fertiliser. Fison's nitric acid plant at Stanford-le-Hope Sprinkle a few iron filings into the non-luminous Bunsen flame.
and (below) combine drilling corn and fertiliser. Sparks are formed as each particle is raised to a white heat. Simi-
ll'OHt
larly, platinum or a porcelain rod become white hot and emit
foil

light when heated a high temperature in the non-luminous Bunsen

to
flame. This principle is used in the incandescent mantle where small
particles of thorium and cerium oxides are suspended in a non-
luminous Bunsen flame.
Hold a cold evaporating dish by means of tongs for a minute in the
luminous Bunsen flame. On removal, the dish will be found to be
blackened by carbon. No such effect is observed if the experiment is
repeated using the non-luminous flame. The presence of the particles
of carbon is thought to be responsible for the luminosity of this type
of flame.
Effect of increase of pressure. Increase of pressure of the gases
taking part in the combustion increases the luminosity of the flame.
The effect of temperature on luminosity. Set up the apparatus of
Fig. 103 with a silica tube extension fitting over aBunsenburnertube.
Open the air holes and obtain the non-luminous flame at the end of
308 A NEW CERTIFICATE CHEMISTRY
the silica tube. Now heat the silica tube strongly with a second
Bunsen burner. As the silica tube is heated, the flame at the end of the
silica tube gradually becomes luminous and luminosity diminishes
as
the tube is allowed to cool.

Chapter 23

Carbonates and Hydrogen Carbonates

CARBONATES
K '(Carbonates Carbonates of these metals'
Fig. 103. Na Jsoluble. not decomposed by heat.
Effect of temperature on luminosity.
Ca Any carbonate
Explosions Mg Carbonates Carbonates of these metals with any acid
Al of these decomposed into oxide of liberates car-
Explosions result from very rapid, exothermic chemical reactions.
Zn ^metals the metal by heat bon dioxide.
Consider a mixture of hydrogen, two volumes, and oxygen, one
volume. If the mixture is sparked, the gases are heated to very high Fe insoluble
Pb in water. (Al forms no carbonate)
temperature near the spark. They combine and liberate heat.
Cu
H, + iO, -> H tO; A// - -286 kJ g-eqn" 1

This heat raises the temperature of neighbouring gas, which com- Ammonium carbonate is also soluble in water.

bines liberating more heat, and so on with great rapidity. The mass The above table summarises briefly the important properties of the
of gas is raised to incandescence in a fraction of a second and the common carbonates.
consequent great expansion produces a pressure wave in the air. The
whole effect is called an explosion. Test for any carbonate
Put some of the suspected carbonate in a test-tube and add dilute
nitric acid. If a carbonate is present there will be effervescence and the
Questions on this chapter will be found on page 317. gas which comes off will turn lime-water milky:
OV" + 2H + -* H O 4- CO, g

Ammonium carbonate (NH 4 ) 2 C0 3

This compound is prepared as a sublimate, by heating ammonium
sulphate with limestone.
(NH 4) 2S0 4 + CaCO s
->- (NH 4) sCO, + CaS0 4
It is used as a constituent of 'smelling salts' and as a chemical reagent.

Potassium carbonate, K 8 C0 3
Potassium carbonate is very similar to sodium carbonate. (See
p. 3 10.) It cannot, however, be made by the Solvay process because
309
310 A NEW CERTIFICATE CHEMISTRY SODIUM CARBONATE 311
the hydrogen carbonate of potassium is too soluble. It is made by the
Sodium hydrogen carbonate is filtered from the white sludge and
Leblanc process and in other ways.
washed free from ammonium compounds. It is then heated to convert
Potassium carbonate differs chiefly from sodium carbonate in that
it to sodium
carbonate and carbon dioxide evolved is used again.
it is very deliquescent, and is anhydrous.

It is used to make soft soap, hard glass and potassium salts gener-
2NaHC0 3 -v Na 2CO s + H a O + CO»
ally. The substance formed anhydrous sodium carbonate, which finds
is

a wide market. form (washing soda) is required, the

If the crystalline

Sodium carbonate (soda ash), \a.,C O anhydrous solid is dissolved in such an amount of hot water that
crystallisation occurs on cooling. The crystals are removed and
Sodium carbonate is obtained in both the anhydrous and crystal-
allowed to dry.
line states by the Solvay process.
Na a CO s I- lOH^O-*- Na 8CO 3 .10H 2 O
Solvay process
Very concentrated brine (28% NaCl) is saturated with ammonia Efficiency of the process
are cheap and
gas in a tower and the ammoniacal brine is run down further Solvay (1) The principal raw materials for the process
towers up which carbon dioxide is forced. The towers are fitted with plentiful. They are sodium chloride and limestone. The common salt

perforated mushroom-shaped baffles at intervals (Fig. 104). These is extracted from deposits as brine; the limestone
yields quicklime

and carbon dioxide when heated.

ammoniacal CaC0 3 ?± CaO + C0 2

Waste 4|| brine Carbon dioxide ispassed to the carbonating tower and approximately
gases half of it is recovered in the heating of sodium hydrogen carbonate
Circular
above.
metal Ammonium chloride, NH/Cl", is left in the solution after pre-
baffles washed out of the
cipitation of sodium hydrogen carbonate or is

precipitate. Ammonia is recovered by heating the solution and wash-

ings with quicklime (above) and returned to the ammonialing tower.
CaO + H 2 -»- Ca(OH) 2
2NH 4 C1 + Ca(OH), -> CaCl 2 + 2H 2 + 2NH 3

Suspension of Consequently, once the pipe-line is full, no further external supplies

carbon
sodium hydrogen ammonia arc theoretically required. In practice, about of the 2%
dioxide of
carbonate ammonium chloride in use is added per circuit to restore manipu-
m lative losses.
The process one of continuous flow and only a minimum
sodium (2) is

hydrogen labour cost.

carbonate (3) The principalweakness of the process is its failure to utilise
Fio. 104. the chlorine of the sodium chloride used. This is lost as calcium
Solvay tower. chloride (see equation in (1) above) for which there is only slight
demand.
baffles delay the flow of liquid and present surfaces for reaction.
Sodium hydrogen carbonate is formed. It is not very soluble in Uses of sodium carbonate
water, so it precipitates; precipitation is assisted by cooling the
Four of the important uses of sodium carbonate are the following.
lowest third of the tower.
(a) Manufacture of glass. Ordinary bottle glass is made by fusing
NaCl + NH OH + CO a -»• NaHC0 + NH 4CI
4 3 together sodium carbonate (or sulphate), calcium carbonate, silica
 312 A NEW CERTIFICATE CHEMISTRY SODIUM CARBONATE 313

and a little carbon (reducing agent). Broken added to

glass (culiet) is In ionic terms:
assist fusion.
20H- + CO, C0 3*"4 H,0 (1st stage)
Na,C0 3+ SiO, -> Na Si0 + CO,
2 3 CO.*-+ HjO + CO, 2HC0 3 - (2nd stage)
CaCO a + SiO, — CaSiO + CO,
»•
a

The mixture of silicates (with some unchanged silica) constitutes the

water to
glass.
(b) Manufacture of water-glass. Sodium carbonate
remove acid
is fused with
silica to produce sodium silicate.

Na,C0 3 + SiO, - Na,Si0 3 + CO,

marble
and dilute
sodium hydroxide
solution
On cooling, a glassy solid is left, which is broken up, boiled with water hydrochloric
and evaporated to a colourless, treacly material, known as water- acid
t/ ice-water
glass. It is used in preserving eggs, in fire-proofing, and in producing
r [.cooling
cements. sodium hydrogen
(c)In domestic water-softening. Calcium ion, Ca 2+ , which is the
principal cause of hardness in water, is precipitated from the water
t carbonate opt.

2_ by the addition of sodium Fig. 105.

as chalk, Ca2+ 3 C0
, carbonate.
Preparation of sodium carbonate.
(d) In the manufacture of sodium hydroxide (Gossage's process).
A 10% solution of washing soda is steam-heated and stirred in an
wash the solid residue two or three times with a little
Filter this off,
iron tank, this metal having no action with sodium hydroxide (the cold water, and then transfer the solid to a dish and heat. Finally
product required). Lumps of quicklime are contained in steel-wire sodium carbonate will be obtained as a fine white powder.
cages which dip into the liquid.
2NaHC0 3 -»- Na,C0 3 + H,0 + CO,
CaO + H,0 -> Ca(OH), Carbon dioxide is evolved during the reaction.
Na,CO s + Ca(OH), -»• 2NaOH + CaC0 3

The second reaction is, in fact, somewhat reversible, but the lower Properties and uses of washing soda
solubility of calcium carbonate (compared with calcium hydroxide) Washing soda is sodium carbonate decahydrate, Na,CO 3 .10H,O,
causes it and so force the reaction to the right (as writ-
to precipitate large translucent crystals.
ten above). This produces a satisfactory yield of sodium hydroxide. Efflorescence. On exposure toairthecrystals lose
weight and become
Calcium carbonate is filtered off under reduced pressure and the coated with a fine white powder which renders them opaque.
Each
filtrate is concentrated by steam heat, also under reduced pressure.
molecule of washing soda has given up to the atmosphere 9 mole-
Solid sodium hydroxide is not produced; the concentrated solution cules of water of crystallisation.
is applied to the required uses. For a laboratory version of this
Na.CO 3 .10H,O-»- Na a C0 3 .H,0 + 9H,0
process, see p. 255. sodium carbonate sodium carbonate
decahydrate monohydratc
Laboratory preparation of sodium carbonate to the
Such an action, that is, the giving up of water of crystallisation

(a) By the action of heat on sodium hydrogen carbonate (see p. 124). atmosphere, is termed efflorescence.
(b) From sodium hydroxide (caustic soda) solution. Fit up the The crystals are readily soluble in water.
apparatus as shown (Fig. 105). Pass carbon dioxide (free from hydro- Anhydrous sodium carbonate can be made by heating the hydrated
chloric acid) into a moderately concentrated solution of sodium sodium carbonate. It is a fine white powder and does not dissolve as
hydroxide for some time until finally a white solid (sodium hydrogen readily in water as do the crystals.
carbonate) appears on the bottom of the boiling-tube. Solutions of sodium carbonate in water are alkaline to litmus.
2NaOH + CO, -> Na,CO s + H,0 (1st stage) This is due to the feebly acid properties of carbonic acid. This acid
is expelled by almost every other acid, and
hence, sodium carbonate
Na,C0 3 + H,0 + CO, -» 2NaHC0 3 (2nd stage)
 :

314 A NEW CERTIFICATE CHEMISTRY ZINC CARBONATE 315

acts like sodium hydroxide, although the former is a salt and the ZnS0 4 + 2NaHCO,-> ZnCO, + Na,S0 4 + H O + CO a a

latter an alkali.
(If sodium carbonate is used, basic carbonate of zinc formed.)
is

Na a CO a + 2HC1 -»- 2NaCl + H aO + CO, The white precipitate is filtered off, washed with hot distilled water
Sodium carbonate can be used quantitatively in volumetric analysis, and allowed to dry.
as if were an alkali.
it Zinc carbonate is attacked by dilute acids liberating carbon
Notice that sodium and potassium carbonates are both soluble dioxide, for example:
in
water and are not decomposed at a red heat. ZnCO, + 2HC1 ->- ZnCl, + H aO + CO,
Sodium carbonate is used for the softening of water for domestic On heating a little zinc carbonate in a test-tube, carbon dioxide is
purposes, and in the manufacture of glass, borax, caustic soda and
given off and zinc oxide (yellow when hot, white when cold) remains
water-glass. It is a constituent of many 'dry soap' powders.
in the test-tube.

Calcium carbonate, CaC0 3 ZnC0 3(c) ->• ZnO(c) + CO,(g)

Zinc carbonate is used medicinally.
This occurs as limestone, marble, chalk, and in many other forms,
and, since it is insoluble, can easily be made in the laboratory by

double decomposition (see p. 233). It is seen as a white precipitate Lead(II) carbonate, PbC0 3
when carbon dioxide is bubbled into lime-water. This is made in the laboratory, as a white precipitate, by adding
Ca(OH), + CO a - CaCOj + H O a
sodium hydrogen carbonate solution to a solution of lead(II) nitrate
calcium in water.
carbonate
(chalk) Pb(N0 3) a + 2NaHCO a -> PbCO + 2NaNO + H O +a s a CO,
The chalk can be obtained by filtering off the precipitate, washing Sodium carbonate precipitates basic lead carbonate.
it a few times with hot water and allowing it to dry. White lead, basic lead carbonate, Pb(OH),.2PbC0 3 is used ex- ,

It is attacked by dilute hydrochloric and nitric acids with the
evolution of carbon dioxide, for example:
CaCOa + 2HC1 -*• CaCl, + H O + CO, a
With dilute sulphuric acid, however, the action slows
finally stops, particularly if the
calcium carbonate is in
for example, marble. The reason
is that calcium sulphate, being only
sparingly soluble, forms a protective layer on the outside preventing
the sulphuric acid from acting upon the solid within.
Although practically insoluble in pure water, calcium carbonate is
dissolved by water which contains dissolved carbon dioxide, be-
tensively as a paint when mixed with oils. It is made by subjecting
strips of lead to the action of acetic acid, water-vapour, carbon diox-
ide and air. It is poisonous and blackens rapidly in industrial areas,
where hydrogen sulphide occurs.
down and N.B. LeadfJI) carbonate is not readily acted upon by either dilute
lump form, hydrochloric or sulphuric acids. A layer of insoluble chloride or
sulphate formed round the carbonate protects it from further action.
Dilute nitric acid attacks it to liberate carbon dioxide in accordance
with the general action of acids on carbonates:
C0 3 2 " + 2H+ H O + CO,
a

cause it forms soluble calcium bicarbonate (hydrogen carbonate).

CaCO s + H a O + CO a -»- Ca(HC0 3), Copper(II) carbonate, CuC0 3
calcium This is made by double decomposition and
it is usually obtained as
bicarbonate
a basic having the formula CuC0 3 .Cu(OH) a . This is a bright
salt,
(See pp. 202-6 for treatment of calcium carbonate under 'hard- green powder which liberates carbon dioxide on being heated, and
ness of water' and 'stalagmites and stalactites'.) black copper(II) oxide is left.
Action of heat on calcium carbonate (see p. 244).
CuCOa -» CuO + CO a ; Cu(OH), -* CuO + H aO
Zinc carbonate, ZnC0 3 It dissolves in dilute acids with the liberation of carbon dioxide, for

This is formed as a white precipitate when sodium hydrogen example

carbonate solution is added to a solution of zinc sulphate in water. CuCO, +H a S0 4 -* CuS0 4 + H O + CO
a a.
316 A NEW CERTIFICATE CHEMISTRY QUESTIONS 317

BICARBONATESor HYDROGEN CARBONATES The white residue is sodium carbonate. This test distin-
guishes sodium hydrogen carbonate from sodium car-
We are only concerned with the hydrogen carbonates of sodium bonate, which is unaffected by heat.
and calcium, all the others being unstable or unimportant.
Sodium hydrogen carbonate is used in the manufacture of baking
Sodium hydrogen carbonate (baking soda), NaHCO . powders. Under the action of heat it decomposes, as above, and
Sodium hydrogen carbonate is manufactured by saturating a wet gives off carbon dioxide which causes the cake to 'rise' and so be
mush of Solvay sodium carbonate and water with carbon dioxide. light. This is why it is commonly called 'baking soda*. Baking powders

The product is washed with cold water and dried. also contain rice powder as a diluent, and tartaric acid (or a similar
compound) to react with the sodium carbonate, which would other-
CO a 8 - + H,0 + CO, -» 2HCO s - wise be left when the hydrogen carbonate decomposes.
Laboratory preparation of sodium hydrogen carbonate
Calcium hydrogen carbonate
Sodium hydrogen carbonate is made in the laboratory by bubbling
carbon dioxide for some time through a concentrated solution in See Hardness of Water, p. 202.
Its method of preparation and its reactions are chemically similar
water of either sodium hydroxide or sodium carbonate (see Fig. 105,
to those of sodium hydrogen carbonate.
p. 313). In the latter case the reaction takes place much more quickly:

CO, + Na,CO a + H,0 - 2NaHCO s

Calcium hydrogen carbonate cannot, however, be isolated as a
solid, since it decomposes too easily, and all its reactions are carried
sodium
out in solution.
carbonate
With sodium hydroxide
QUESTIONS ON CARBON, CARBONATES AND OXIDES
2NaOH 4- CO,-*- Na,CO a + H,0 OF CARBON; FLAME
sodium
hydroxide 1. Graphite is called an 'allotropic form' of carbon. What do you under-
stand by this statement? Give one other example of allotropy. How would
then Na,CO a + H,0 + CO, -> 2NaHC0, you prove by a quantitative experiment that the statement is correct in the
In both cases the hydrogen carbonate is deposited as a white case of graphite and pure charcoal ? (N.U.J.B.)
powder and this is filtered ofT, washed two or three times with a little
2. What is the action of (a) carbon dioxide; (6) steam, upon red-hot
carbon and what is the practical importance of these reactions? (O. and
cold distilled water, and allowed to dry.
C.)
With dilute acids, the hydrogen carbonate liberates carbon 3. What are the general methods employed for the preparation of
dioxide: metallic carbonates?
5 g of a mixture of anhydrous sodium carbonate and sodium bicarbonate
HC0 3
- -f H + -*• H,0 + CO, were heated until there was no further loss in weight. The resulting solid
weighed 3.84 g. Find the percentage weight of the normal carbonate in the
Action of heat on sodium hydrogen carbonate
mixture. (Na -
= 23; C 12.) (L)
Place a small amount of sodium 4. How does calcium carbonate occur in nature? Describe qualitative
Sodium
Bicarbonate hydrogen carbonate in a dry test- and quantitative experiments which you would do in order to determine
tube and heat gently with the lip of the composition of this substance. (L.)
the tube projectinginto a boiling-tube 5. Describe the preparation of a pure dry specimen of carbon monoxide.

containing lime-water (see Fig. 106). From carbon monoxide how would you prepare and collect a pure
specimen of carbon dioxide? (C.)
A gas is given off which turns the
6. Describe how you would find by experiment the weight of carbon
lime-water milky and is, therefore,
dioxide that can be obtained from 1 g of calcium carbonate.
Lime-water_ carbon dioxide. Water is seen to
turns mi/ky How would you prove that the gas obtained from calcium carbonate is
condense on the cooler parts of the identical with that produced when carbon is burnt? (O. and C.)
Fio. 106.
tube. 7. Describe the preparation and collection of carbon monoxide and
Action of heat on sodium compare its properties with those of carbon dioxide. What would be the
bicarbonate. 2HCO," -> C0 3 2 - + H,0 + CO, result, in the case of each oxide, of passing it (a) over heated copper(II)
 318 A NEW CERTIFICATE CHEMISTRY
oxide; (b) oyer the red-hot charcoal (c) into cold, dilute sodium
; hydroxide
solution? (B.)
8. When oxalic acid is heated with concentrated
sulphuric acid a mixture
of the two oxides of carbon is evolved.
Give a detailed account of how you would:
a s Pccimen of P urc carbon dioxide from this mixture.
ill tEfaS
(b) Find the percentage by volume of each gas in the
mixture. (O.)
Chapter 24
9. Describe carefully an apparatus by which
you could collect for
examination the products of the action of steam on red-hot carbon.
Describe how you would identify each of the products of the reaction.
Of what importance is the reaction in industry? (C.)
Organic Chemistry
10. How is carbon monoxide prepared ? Describe the
chief properties of
this compound. What volume will be found after
the explosion of a
mixture of one volume of carbon monoxide and ten volumes of air?
(You
may assume air to contain one-fifth by volume of oxygen.) (O. and C.)
11. Describe how you would prepare sodium
ORGANIC chemistry is the chemistry of the compounds of
hydroxide from sodium carbon; that is, all organic compounds contain carbon with,
carbonate.
State clearly how you could: also, one or more other elements— hydrogen, oxygen, chlorine,
(a) Distinguish sodium carbonate from sodium hydrogen nitrogen and metals. Carbon shows exceptional behaviour, in a
carbonate;
(p) Prepare sodium hydrogen carbonate from sodium carbonate. (O.) chemical sense, by forming chains of its atoms (sometimes of very
12.Write a short essay on •Flames', with special reference to those
of great length, e.g., about 2000 carbon atoms in polythene) and rings
hydrogen and coal-gas (luminous and non-luminous). (O.)
of its atoms. Sometimes, the chains and rings are included in the same
13. Describe, using diagrams, the structure of
the flame of a Bunsen molecule. Consequently, carbon produces a very great number of
burner. How do you account for the differences in the
flame when the air compounds, many of them very complex, and it has become neces-
holes of the Bunsen burner arc closed? Indicate experiments
which might
be carried out in support of your answer. (L.) sary to make a separate study of these compounds as organic chem-
14. What views were formerly held as to the nature of combustion, and istry. Nominally, every compound of carbon is an organic compound.
what led to their overthrow? Who first gave the true explanation of com- For and conventional reasons, however, a few of the simpler
historical
bustion? carbon compounds, such as carbon dioxide and sodium carbonate,
State clearly all that you believe to be taking place in the burning
candle. (L.)
of a are usually studied with non-carbon compounds in inorganic chem-
istry. Examples of chain and ring formation by carbon atoms will be
15. Starting with solid sodium hydroxide, describe
how you would pre-
pare in the dry solid state (a) sodium carbonate; (h) sodium hydrogen found in the present chapter.
carbonate. Give two tests by means of which you could distinguish
between
these compounds. Describe and explain what happens
when crystals of HYDROCARBONS
washing soda are exposed to the air. (L.)
16. Explain fully any four of the following:
(a) Why a Bunsen burner Hydrocarbons are compounds containing hydrogen and carbon and
strikes back'; (b) the comparatively low percentage
of carbon dioxide in
the air; (t) the difference in the bleaching action of chlorine and no other element. That is, a hydrocarbon has the molecular formula,
sulphur
dioxide; (rf) why sodium sulphate dissolved in water increases
its con-
C x H y x and y being whole numbers. For example, methane, CH 4
, ,

ductivity ;(e) how the flameof a candlediffers from the flameof

hydrogen. (L.) ethylene, C S H 4 and benzene,
, QH
4 are hydrocarbons.
,
The last is the
1 7. What is flame? By means of three labelled sketches only compare the liquid known to the motor trade as benzol.
structures of (a) a hydrogen flame; (b) a luminous
Bunsen flame- (c) a
candle flame. How would you demonstrate the presence of unburnt
gas in
a candle flame, and that this unburnt gascan be used asareducing agent Paraffin Hydrocarbons or Alkanes
?(L.)
18. Powdered marble is strongly heated in the
open air until no further
change occurs. Explain what happens and give three tests proving that the The members of this group of hydrocarbons (also called simply
resultant residue is different from the powdered marble.
Give short paraffins) are distinguished by possessing the general molecular
accounts of two important uses of the residue. Why does a precipitate
formula, C,,H M+8 where n is 1, 2, 3, etc., for successive members of
,
form when temporarily hard water is boiled? How does the impurity
the water in the first place? (L.)
enter the group. This general molecular formula will be justified after the
properties of a typical member of the series have been studied. The
319
 320 A NEW CERTIFICATE CHEMISTRY HYDROCARBONS 321
first member of the series {n = 1) is methane, CH 4, and the second Methane is the important constituent of natural gas which usually
(n = 2) is ethane, C,H 4 Both
. are gases at room temperature and accompanies petroleum deposits. This gas is at present being im-
pressure.
ported into Britain in pressurised tanker ships, as liquid, from the
Laboratory preparation of methane Saharan oilfields and added to coal-gas supplies. Recent borings in
the North Sea have revealed reserves of natural gas estimated (May
Sodium acetate (anhydrous) is ground with its own weight of
1969) to yield at least 3000 million cubic feet of the gas per day for
soda-lime. The mixture is heated in a hard-glass flask (Fig. 107).
Methane is evolved and collected over water. When heating is many years; this daily output would meet the whole of Britain's
current need of gaseous fuel. Several years will be required for laying
finished, the delivery tube must be removed from the water
at once; pipe-fines and for modifying or replacing gas appliances to corres-
otherwise, water may suck back into the hot flask and cause
an pond with the fact that, volume for volume, natural gas has twice
explosion. Soda-lime acts as a source of sodium hydroxide.
the calorific value of present gas supplies. Natural gas is non-poison-
CH 3 COONa(c) f NaOH(c) -> Na 2 C0 3 (c) + CH 4 (g) ous and has no smell, unless hydrogen sulphide is present.
Sodium Acetate and (2) With chlorine. Methane reacts (slowly at ordinary temperature)
Soda - time
with chlorine, the reaction being catalysed by light (photocatalysis).
Methane The first product is monochloromethane, 3 C1
CH
(or methyl chloride,
_
the group, CH
3 , being known as methyl).

CH +4 Cl 2 ->- CH 3C1 + HC1

In a similar way, excess of chlorine may produce, with increasing
difficulty, dichloromethane, CH
2C1 2 , chloroform, CHC1 3 , and carbon

tetrachloride, CC1 4 .

These are called substitution reactions because chlorine successively

replaces hydrogen in the methane molecule. Notice that the hydrogen
is expelled in combination with chlorine as HCI, not as free hydrogen.
Fig. 107. The above two reactions are the only ones given by methane or
Preparation of methane.
other paraffins in ordinary conditions, i.e., without the use of high
Properties and reactions of methane temperature and pressure or other exceptional means. That is, the
Physical properties paraffins area rather inert group; in fact, their name was coined
from the Latin, parum, little, and affinis, affinity.
Methane is a colourless gas with no smell. It is almost insoluble
and much less dense than air in
in water the same conditions (V.D. of Structure of alkanes
methane is 8, of air is 14.4). In the alkane, all carbon atoms exercise a covalency of 4. The

Chemical reactions simplest alkane has, therefore, the molecular formula, 4 , and CH
ismethane. Each covalent bond represents a shared pair of electrons,
(I) Combustion. Methane burns (or explodes) in air on the
appli- one each from the carbon atom and a hydrogen atom. In more
cation of a flame (or electric spark). It produces carbon dioxide
and complex alkanes, carbon atoms form chains by combining together
steam.
by covalency. With chains of two carbon atoms {ethane, C 2 g ) and H
CH4 + 20 -y C0 + 2H
2 2 2 0; A// = - 79 kJ g-eqn" 1 H
three carbon atoms {propane, C 8 8), the molecular structures are
This is an exothermic reaction, utilised as a means of industrial
and shown below, together with methane.
domestic heating when methane is burnt as a constituent of coal-gas. H H H H H H
Similarly, other (liquid) alkanes are used as petrol or fuel oil in
exothermic combustion with air. H—C—H
I
1 C—
H—C— 1 H—C—C—C—
For example, pentane, a constituent
of petrol, burns in the following way.
QH + 80 I2 2 -> 5CO t + 6H 2 with heat evolved
k
methane
kk
ethane
kkk
propane
322 A NEW CERTIFICATE CHEMISTRY HYDROCARBONS 323

Much longer chains are also produced, such as the following: in vigour. For example, all alkanes burn in air and give substitution

HHHHHHHHH reactions with chlorine (p. 320).

(4) The physical properties of
members change gradually in the

hO-UXU-A-U-h same direction along the

and freezing-points rise (CH 4 a gas; —
C
the alkanes, boiling-points
series, e.g., in

s H ia
- a liquid; C8oH 4a —
densities increase
solid, at ordinary temperature and pressure). Also,
and solubility in water decreases as the number of carbon atoms per
In such structures,it will be seen that all the carbon atoms except
molecule increases.
the two ends of the chain use two units of valency to attach
at the
preparation are known which can be
(5) General methods of
themselves to the carbon atoms on each side, so forming the carbon
applied to any member of the series.
chain. Each carbon atom (except the end ones) then has two units of
Other homologous series are alkene hydrocarbons, C„H 2 „, alcohols,
valency left to combine with two hydrogen atoms. That is, except
C„H 2B+1OH, and fatty acids, C„H 2n+1 CO a H. These series are con-
for the end carbon atoms, the relation of carbon to hydrogen is
sidered in the present chapter.
C n H sn But each of the end carbon atoms uses only one valency unit
.

in forming the chain and so can combine with an extra hydrogen

Cyclic compounds
atom, so producing the general molecular formula, C„H 2n+2 . Many alkanes,
alkancs have a branched carbon chain such as the following. In addition to producing open chains of atoms, as in the
carbon can produce closed rings of atoms. Compounds possessing
H H H H H H H such carbon rings arc said to be cyclic
compounds. The commonest rings are
H-C-t-t—C-C~( those composed of five or six carbon
.about 109°
atoms. This is so because the four
H H H H H H
H—C— valencies of the carbon atom are direc-
tional and distributed symmetrically in
H—C—
I

three-dimensional space (Fig. 108). This

gives a natural angle of about 109°
A between any pair of valency directions. Fio. 108.
The angles in a regular five-membered Valency directions of the
In this case, a hydrogen atom is lost from the carbon atom on which carbon atom.
ring are 108° and in a regular six-
the branching occurs. But it is restored at the open end of the branch,
membered ring are 120°. That is, the
so the general molecular formula is unchanged. directions needs very little
natural angle between the carbon valency
American petroleum consists largely of these alkanes from pen-
strain to form 5- or 6-membered rings.
tane C5 H,., to the very complex compound, C43 Hgg. The four is the 6-membered ring of benzene, C„H 6 and
The most important ,

simplest alkanes are allgases in ordinary conditions, i.e., 4 -C 4 10 . CH H derivatives. This usually represented with alternate single and
is
Butane, C 4 H 10 is supplied in pressurised containers as color gas.
its
though
carbon-to-carbon valency bonds (Kekule's formula),
,
double
this representation is known to be unsatisfactory in some respects.
Homologous series

A series of compounds related to each other as the alkanes are

(above) is called a homologous series. Such a series has the following
characteristics.
(1) All members conform to a general molecular formula, e.g.,
for alkanes, C„H W _ S .

(2) Each member differs, in molecular formula, from the next by

aniline,
CH„ alkanes are CH C C3 H8 and so on. Derivatives of benzene are very important chemicals, e.g.,
e.g., 4, 2 H„,
OH, which can be obtained
(3) All members show similar chemical reactions, though varying Cg 6 H NH
B
and phenol,
,
C,H 6
both of
324 A NEW CERTIFICATE CHEMISTRY ISOMERISM 325

from More complex benzene derivatives include

coal-tar as source. Isomerism is the occurrence of two or more compounds
the M. and
B. drugs, aspirin, and a wide range of dye-stuffs. Cyclic with the same molecular formula but different molecular
compounds may also contain straight carbon chains, too, which are structures.
known as side-chains in this case. An example is the following.
Isomers of the same molecular formula have different physical and
CH
chemical properties because of structural differences.
HC/\C-CH,-CH -CH 1-CH 8NH 8 1
HCsJCH Isomers of molecular formula C 4 H 10
CH H H H H H H H
It
is
is obvious that such combinations may become very complex. This
why carbon appears to be the only element which can supply the
H-C-C-C-C-H H— —A-C-H
I
J
very varied and complex compounds needed by living organisms to I

H H H H H H
carry on their vital processes.
H- -H
Petroleum
American petroleum consists mainly of alkanes from QH L
12 pen- ,

tane, to C^Hgg, usually associated with salt water and the gaseous
orCH 3 .CH 2 .CH 2 .CH 3 or CH 3
.CH(CH 3 ).CH 3
paraffins. After removal of impurities (mainly sulphur compounds),
normal butane; a straight carbon isobutane; a branched carbon
the petroleum is distilled into four fractions:
chain. chain.
Up 200°C
to Naphtha 1 QH -C lt H M
lt
20O-260°C Kerosene C 12 H M -C 1S H 31
26O-300°C Gas-oil C 16 H 3!-C 17 Hs, These compounds differ in boiling-point, freezing-point and density.
Above 300°C Fuel oil Their chemical reactions are not very different because they both
Redistillation of naphtha
yields petrol, b.p. 50°-60°C, mainly C H belong to the alkane homologous series.
5 1S
to C,H g0 Other
. products of redistillation of the other fractions are
paraffin, lubricating oil, petroleum jelly and paraffin wax. Much of the Isomers of molecular formida C 2H O
gas-oil fraction is cracked to yield more petrol, i.e., the complex
H H H H
molecules are broken down into simpler units. At about 12 atm pres-
sure and 520°C, gas-oil yields petrol hydrocarbons and valuable H-C—C-O-H H-C-O-C—
alkene by-products, e.g., ethylene, C,H«, and propylene, C 3 6 . (For
fractional distillation, see p. 218).

C lsH at —* CgHjg -f 2C aH« -f C3He

H

or CH 3
H
.CH 2 .OH or CH 3
A
.O.CH 3
H

Petroleum refining occurs usually on an estuary, e.g., at Fawley dimethyl ether; the oxygen
ethanol; an alcohol. The oxygen
(Southampton), to avoid land transport of bulky imported oil and atom forms a bridge between
atom is part of a hydroxyl
to secure large flat areas for its storage, segregated because of fire the two carbon atoms. There
group, OH.
risks.
is no hydroxyl group.

Isomerism
Ethanol is a liquid, dimethyl ether a vapour at room temperature and
Isomerism occurs often among organic compounds because of
pressure. alcohol, ethanol reacts rapidly with sodium and
As an
their complexity.
phosphorus pentachloride (p. 335). The ether has neither of these
1 reactions.
For naphtha as a source of fuel gas, see p. 292.
326 NEW CERTIFICATE CHEMISTRY
A ETHYLENB 327
Isomers of molecular formula C 2 H 4 CI concentrated sulphuric
2
shaking and cooling under the tap, is added
H H H H 3
acid (100 cm ). Apparatus is set up as in Fig. 109, and the mixture is

with care to about 180°C. Ethylene is evolved and collected

heated
CI— c—c—ci H—C—C—CI
or CH 2
u
C1.CH 2 C1. or CH 3
u
.CHCI 2 .
over water. The wash-bottle of alkali solution
phur dioxide, a by-product
reduces the sulphuric acid
produced
slightly.
in small
serves to remove sul-
amount

The alcohol and acid first produce ethyl hydrogen sulphate.

as the alcohol

One chlorine atom combined HO

with each carbon atom.
is Both chlorine atoms are com- C.H.OH + H S0 -> C H
2 4 2 5 .HS0 4 r- a
bined with the same carbon
When heated, ethyl hydrogen sulphate releases ethylene.
atom.
C a H s .HS0 4 -> H 2 S0 4 + C H4
2
These compounds boiling-point alcohol by
These two reactions are equivalent to the dehydration of
differ in and freezing-point. If
hydrolysed, the left-hand one yields glycol, C 2 H 4 (OH) 2 ; the other the acid.
yields aldehyde, CH 8 .CHO. C 2 H sOH-H 20->-C 2 H 4
Industrial production of ethylene
define Hydrocarbons or Alkenes
the gas-oil fraction
In industry, ethylene is produced by cracking
The define hydrocarbons (or alkenes) are members of a homo- At 12 atm pressure and 520°C, alkanes
from distillation of petroleum.
logous series of general molecular formula, C„H . That is, each H together with
2B in the petrol range (C S H, S C B 20 ) are produced,
member of the series has two fewer hydrogen atoms per molecule
ethylene and, possibly, other alkenes. For example,
than the corresponding alkane, e.g., alkane, C
8 H
8 , alkene, C s a The H .
C„H M -* C 8 H 18 + 3C 2 H 4 + C 8 H 6 .

reason for this will be mentioned later. The most important

alkene
is ethylene, C
2 H
4 , which is a gas at room temperature and pressure. Properties and reactions of ethylene
Physical properties. Ethylene is gaseous at room temperature
and
Laboratory preparation of ethylene (or ethene)
less dense
pressure, colourless, almost insoluble in water and
slightly
Ethylene is usually prepared by the dehydration of ethanol (alcohol)
(V.D. - 14) than air (V.D. = 14.4).
by hot, concentrated sulphuric acid. To ethanol (50 cm 3 ), slowly with
Chemical reactions
(or
(1)Combustion. Ethylene burns (or explodes) in air if a light
electric spark) is applied. The products of complete
combustion are
I80°C
carbon dioxide and steam, but the flame tends to be smoky from
in ethy-
Cong. Sulphuric unburnt carbon because of its high proportion (about 86%)
acid and ^J lene.
Ethanol
C 2 H 4 + 30. -»- 2CO, + 2H t O
Ethylene number of addition re-
(2) Addition reactions. Ethylene gives a
actions in which two hydrogen atoms (or their equivalent) are taken

into combination per molecule of ethylene to

form a single product.
said to be unsaturated. Structurally, this means
Ethylene is, therefore,
that contains a double bond between carbon atoms, H 2 C
it
2. ^CH
This will be further considered later.
(a) With chlorine or bromine. With
chlorine at ordinary tempera-
ture, ethylene combines rapidly to give an oily liquid, ethylene
Fio. 109. dichloride.
Preparation of ethylene. H 2C=CH 2 + CI,-* CH.Cl.CH.Cl
328 A NEW CERTIFICATE CHEMISTRY POLYTHENE 329

This accounts for the name, defiant gas, by which ethylene was once Polythene
known, from Latin, oleum, oil, andy?o, I become. The term, define,
If ethylene, with a trace of oxygen present, is pressurised to about
has developed from the older name.
1000 atm and heated to start the action, it is polymerised to form
The similar reaction with bromine vapour rapidly destroys the polyethylene or polythene. Polymerisation is the combination of two
reddish-brown colour of the vapour. This acts as a distinguishing
or more molecules of a given compound to form one complex mole-
test between ethylene and gaseous paraffins, e.g., methane or ethane, of material.
cule with no gain or loss
which do not give this rapid colour change.
nA—* A„
H 2C=CH, + Br 2 -> CH 2 Br.CH 2 Br
The product, A„, ispolymer of the original compound, A.
called a
With hydrogen iodide. Ethylene combines rapidly with hydro-
(b)
polymerisation is quite exothermic and,
In the case of ethylene, the
gen iodide (vapour) at ordinary temperature to produce ethyl iodide. cooling required.
once the reaction has started, is

H,C=CH + 2 HI -J- CH 3 .CHJ(or C H6 I)

2
Polythene is very resistant to the common types of chemical action
The group, C,H 6 -, is called the ethyl group. The gases, HBr and HC1, and can be moulded (while hot) into a great variety of domestic and
scientific articles- buckets, bowls, bags, flexible containers, funnels;
combine similarly but more slowly.
With concentrated sulphuric acid. Ethylene is absorbed rapidly
(c) wash-bottles. The polymerisation can be stated as:

by this acid at room temperature to form ethyl hydrogen sulphate. 3n(CH 2 =CH 2 ) ->- (-CH 2-CH 3 -CH 2-CH 2 -CH 2-CH 2 -)„
H C=CH, + H S0
2 2 4
-»- CH 3 .CH HS0 4 (or QHb.HSOJ
2 where n about 300. From this, polythene resembles a highly com-
is

The is reversed at about 180°C, liberating ethylene.

action plex alkane and shares the chemical inertness of this group.
(d)With hydrogen. Ethylene combines with hydrogen if the two
are passed over finely divided nickel (catalyst) at about 200°C. The
Unsaturation in ethylene
product is the alkane, ethane.
Ethylene is said to be unsaturated because one molecule of it can
H C=CH, + H
2 2
-*- CH 3 .CH S (or C 2H,) combine with two hydrogen atoms (or their equivalent) in addition
This (Sabatier's) reaction is important as representing the essential reactions. In general,
change in the conversion of oils into margarine. An oil possesses a
long carbon chain (15-17 atoms) in which there is one ethylenic
H 8C=CH + 2 A.B - AH C-CH B
2 2

double bond,— CH=CH—

Pressure is used (5 atm) and a somewhat
. where A and B are univalent atoms or groups. Several examples of
lower temperature (180°C) and the oil is hydrogenated in the presence these reactions were given in the recent sections of this chapter. The
of nickel. This saturates the double bond, so converting the oil into C to C double bond which represents this unsaturation indicates that,
a fat, which is then sold as margarine. between the carbon atoms concerned, two pairs of electrons are
—CH=CH— + H 2 -* —CH a—CH»— shared in covalency.

(e) With potassium permanganate. Ethylene reacts rapidly if shaken H H H H

with potassium permanganate solution at ordinary temperature. If
acidic, the solution is decolorised, being
if alkaline, it
reduced to a manganese salt;
turns green, being reduced to a manganate. In both cases,
u corresponds to
oo o oo
CSC
oo o oo
H H
the ethylene is converted to ethylene glycol by water and oxygen from
the permanganate.
When the addition reaction has taken place, e.g., with Cl 2 , only two
H,C=CH, + H 2 + (O) ->• C,H 4 (OH), electrons are shared between the carbon atoms; only single covalent
This reaction distinguishes ethylene from all gaseous alkanes, e.g.,
I
bonds are present in the molecule, the compound is said to be satur-
ated and an alkane derivative. It gives no addition reactions but
methane or ethane, which have no reaction with permanganate. is

Ethylene glycol is the material used in anti-freeze solutions for motor- reactsby substitution. The addition of chlorine to ethylene is shown
car radiators and for the production of terylene (p. 337). by the following equation.
330 A NBW CERTIFICATE CHEMISTRY ACETYLENE 331

H H H H PH
3 , is absorbed by the
acidified

u + CI a CI—C—C—CI
age. The
chief impurity phosphine,
copper(II) sulphate solution. Acetylene is collected over water.

A k n CaC
Properties of acetylene
2 (c) + 2H 2 -> Ca(OH) 2 + C H 8(g)

Physical. In ordinary conditions, acetylene is a colourless gas,

a

Acetylene or Ethyne
almost insoluble in water and having a sweet smell when pure. It is
Acetylene is really the first member of a homologous series of slightly less dense than air (V.D. is 13; V.D. of air is 14.4). Acetylene
hydrocarbons called the alkynes. The general molecular formula of is strongly endothermic.

the series is CH^-,. For acetylene itself, n =

2, and the molecular 2C H, ->
+ t; QH AH = +
200 kJ g-eqn" 1
formula is C 2 H 2 So far, acetylene is the only member of the series
. Like endothermic compounds in general, it is rather unstable and
which has acquired general importance. Alkynes are characterised liable to explode if stored under compression alone. For industrial
by possessing a carbon-to-carbon triple bond at one point in the purposes, it is stored in steel cylinders in solution in acetone at about
carbon chain. The triple bond involves the loss of four hydrogen 12 atm pressure.
atoms per molecule in an alkyne hydrocarbon when compared with Chemical reactions. Having a carbon-to-carbon triple bond in its
the corresponding alkane. structure, acetylene an unsaturated compound. It gives a number of
is

addition reactions, combining with four hydrogen atoms per molecule

(or their equivalent) as a maximum, then producing the saturated
H—Ci=C— alkane, ethane, or one of its derivatives. These reactions are of the
type:
acetylene H H CH CHA,
ethane + 2AB —* |
where A and B are univalent

The triple bond involves the sharing of three pairs of electrons in

CH CHB a
covalency between the two carbon atoms. Notice that the two A groups usually combine with the same carbon
atom, as do the two B groups. Compounds of the type CHAB.
Preparation of acetylene CHAB are rarely produced.
(a) With bromine. At ordinary temperature, acetylene
combines
For apparatus, see Fig. 110. Cold water is dripped on to calcium
carbide. Much heat is evolved and sand protects the flask from break- rapidly with bromine, forming acetylene tetrabromide.
CH CHBr 2
Water HI +2Br t ->|
CH CHBr 2
Copper Sulphate Chlorine gives a corresponding reaction provided it is diluted with
in dil. Sulphuric an inert gas, but, if pure acetylene and chlorine are mixed, a violent
acid
Acety/ene explosion occurs, with formation of carbon and hydrogen chloride.
H +
C 2 f Cl 2 -»-2C 2HCl +
Calcium (b) With hydrogen. If passed with twice its own volume of hydrogen
Carbide Water over nickel (catalyst) at about 200°C, acetylene forms ethane.
C,H 2 + 2H -*C 2H
2 8

With halogen acids (as gases). Acetylene combines readily with

(c)
Sand hydrogen iodide at room temperature to form ethylidene iodide.
CH CHI,
Fio. 110. + 2HI ->-
Preparation of acetylene. :H
ft ch,
 332 A NEW CERTIFICATE CHEMISTRY ALCOHOLS 333

A corresponding reaction is given by hydrogen bromide at I0O°C, much of it remains unburnt unless special means are used to provide
but the reaction with hydrogen chloride is very slow. a good air supply.
(d) With water. Acetylene reacts additively with water if passed 2C 2 H 2 + 50 t -> 4CO a + 2H O s
into dilute sulphuric acid at about 96°C with mercury(II) sulphate
A flame of acetylene burning in oxygen (the oxyacetylene flame) is
present as catalyst. The product is aldehyde (acetaldehyde). used in welding
very hot and can give a temperature of 2200°C. It is
C 2 H 2 + H 2 -y CH3.CHO and in cutting up steel scrap.

This is the first stage of the manufacture of acetic acid from acetylene
(p. 338).
Manufacturing uses of acetylene
(e) With acidified potassium permanganate solution. At room tem- Acetylene has recently become very important as a source of organic
perature, with shaking, acetylene quickly decolorises this solution chemicals on the large scale, though some of the products made from
(i.e., reduces it) with formation of oxalic acid. it are very complex. The
manufacture of aldehyde and acetic acid from
acetate,
8Mn0 4 ~ + 5C a H + 24H+ acetylene is given on p. 338. It is also polymerised to ethyl
a
-*• 5H 2 C 2 4 + 8Mn 2+ + 12H 2
aluminium ethoxide as catalyst at 0°C.
using
Notice that acetylene decolorises bromine vapour (see (a) above)
and decolorises acidified permanganate solution (see (e) above). These
2CH3.CHO -> CH 3 .COOC sH 8
reactions distinguish it from alkanes such as methane and ethane Acetylene can also be converted to acetic anhydride, which, together
cellulose to
which do not give these changes; they do not distinguish acetylene with acetic acid (also an acetylene product), converts
cellulose acetate which is used as celanese rayon and
cellophane.
from ethylene which also produces the same colour changes (p. 327).
Acetylene is also the starting material for making polyvinyl chloride,
Metallic derivatives of acetylene which is used in electrical insulation and waterproofing, and polyvinyl
acetate, which is used in sheets as the middle layer of
Triplex safety
Acetylene produces several metallic derivatives, cuprous or copper(I)
glass. The uses of the oxyacetylene flame have been mentioned above.
acetylide and silver acetylide being the most important.
Copper 1 1) acetylide. If acetylene is passed at room temperature into
a solution of cuprous chloride in ammonia, a reddish-brown precipi- ALCOHOLS
tate of copper(I) acetylide is at once thrown down.
The alcohols form a homologous series of general molecular for-
C,H, + 2CuCl + 2NH OH -»• Cu C 2 + 2NH 4 CI + 2H
4 2 2 mula C„H 2n+1 OH (or C n H ani2 0). The first of these formula; is usually
Silver acetylide. If acetylene passed at room temperature into a
is preferred because shows the presence of the hydroxyl group, OH,
it
solution of silver oxide in ammonia, a yellow precipitate is produced, which is the characteristic group of the alcohols. The first two mem-
rapidly turning grey. It is silver acetylide. bers of the series are methanol, CH 3 OH, also known as wood spirit

C 2 H„ + Ag s O -»• Ag 2 C 2 + H,0 because of its early production by distillation of wood, and ethanol,
C 2 H sOH, the alcohol of ordinary life. The two are also known
If allowed to dryand heated, both acetylides are explosive, the silver
(respectively) as methyl alcohol and ethyl alcohol.
salt much more violently. Both give off acetylene if warmed with
dilute acid.
Ethanol
Ag 2 C 2 + H S0 4 ->- Ag 2 S0
2 4 -f C t H,
Manufacture of ethanol
The two reactions above distinguish acetylene from ethylene which
By fermentation. The source of the alcohol is some form of
forms no metallic derivatives. (1)
starch; in western Europe, potatoes are commonly used. They are
Polymerisation. Acetylene polymerises into the cyclic hydrocarbon,
benzene, if passed through a tube at red heat.
pressure-cooked to release the starch granules and then treated with
malt (partially sprouted barley) for an hour at 60°C. Malt supplies an
3C 2 H 2 —> C,H„ enzyme, i.e., an organic catalyst, called diastase. In these conditions,
Combustion. Acetylene burns in air if ignited by a flame or electric the starch is hydrolysed to a sugar, maltose. The empirical formula
spark and mixtures of the two can explode very violently. The flame C 8Hi O
of starch is 5.
is usually very sooty; acetylene contains over
90% of carbon and 2C,H 10 O s +H 2
-»- C 12 H 22O n (maltose)
 334 A NEW CERTIFICATE CHEMISTRY ALCOHOLS 335
At room temperature, yeast is added. One of its enzymes, maltose, In a newer process, ethylene and steam are passed over phosphoric
catalyses the hydrolysis of maltose to glucose. acid (catalyst) at 600°C and 60 atm pressure. The greater part of the
C„H u O u + H.O -> 2C„H I2 world's industrial ethanol is now produced by these two processes.
8
The alcohol is used as a solvent in stains and polishes and in the
Another enzyme of yeast, zymase, catalyses the decomposition of
manufacture of essences, perfumes and drugs. Its use in beverages and
glucose to ethanol and carbon dioxide.
methylated spirit was mentioned above.
C 6 H 12 0, -*- 2C 2 H sOH + 2CO,
The 'wash*, containing less than 11% of ethanol, is converted by dis- Properties of alcohols
tillation in a very efficient still to a liquid containing about 95% of Physical. The simpler alcohols, e.g., methanol and ethanol, are
ethanol and this is the purest form (surgical spirit) in which liquids at room temperature and pressure, volatile, colourless and
the
alcohol is usually sold. The material known as methylated spirit con- possessed of a characteristic smell. They mix with water in all pro-
tains about 85% of ethanol (with water) and has paraffin portions. Some alcohols are known with a carbon chain of about
and colour-
ing matter added to prevent its being drunk or used for
chemical 20 atoms. These are solids resembling paraffin wax in appearance.
manufacture to evade excise duty. Chemical reactions. (1) Reactions of the hydroxy I group. All alco-
Fermentation of starch (or the sugar of grapes) produces many hols contain the hydroxyl group, OH, and show corresponding
alcoholic beverages, e.g., varieties of beer and wines with 8-20% reactions.
of
alcohol; fermented and distilled products are known as spirits— (a) With sodium. If added to 1-2 cm 3 of
a small piece of sodium is

whisky, gin, brandy, rum— and contain about 30% of alcohol. ethanol at room temperature, effervescence will occur with liberation
The effect of alcohol on human capabilities is, of course, attracting of hydrogen (explosion on the application of a flame). Sodium ethoxide
much contemporary attention, especially in its relation to motoring. will eventually remain as a white, deliquescent solid. Methanol
The fact appears to be that even a little alcohol tends to impair skill behaves similarly.
and cloud judgement, though the extent of these effects depends
the individual and his alcoholic experience. Greater
on 2C 8 H 6OH + 2Na -»- H a + 2C a H 6ONa (sodium ethoxide)

alcohol lead to much greater lack of muscular control,

quantities of
2CH aOH + 2Na -* H 8 + 2CH ONa3 (sodium methoxide)
e.g., the
drunken stagger, and, ultimately, to coma, the state of dead-drunk. (b) With a chloride of phosphorus. If a little phosphorus penta-
A sufficient large alcoholic consumption may lead to continuance of 3
chloride is added to 1-2 cm of ethanol at room temperature, a
the coma to the point of death. Methanol is
more poisonous still: vigorous reaction occurs with liberation of 'steamy' fumes of hydrogen
even moderate amounts may affect the optic nerve and
produce blind- chloride. The organic product is ethyl chloride, which escapes as
ness for several days, while greater amounts may produce
permanent vapour. This is the recognised test for the hydroxyl group, OH, in a
blindness or prove fatal. straight-chain organic compound. Its effect is to replace the OH
The breaking down of a complex material such as starch into much group by CI.
simpler substances, e.g., by fermentation into alcohol
and carbon C a H sOH + PC1 B
->- C 2 H 5C1 + POCl 3 + HC1
dioxide, is known as degradation and is a common way
of utilising
natural products. The distillation of coal in air-free
retorts to yield
Methanol, CH sOH, gives a similar reaction to produce methyl chlor-
coal-gas, tar, coke and ammonia liquor is
another example of de- ide,CH 3C1, which is also a vapour.
gradation. Phosphorus trichloride gives a similar reaction, but usually less

(2) Manufacture of alcohol from petroleum products. The cracking vigorously.

of petroleum oils to produce ethylene was described
on p. 327 If 3C 2H 5 OH -f 2PCl 3 -> 3C SH 6 C1 + P,0 3 + 3HC1
ethylene is absorbed at 80°C under slight pressure in
concentrated
sulphuric acid, ethyl hydrogen sulphate is formed. All members of the alcohol homologous series give the reactions (a)
If this product is
diluted with water and distilled, ethanol is obtained. and (b) above, though with decreasing vigour as the number of
carbon atoms increases.
C,H« + H g S0 4 QH 5 .HS0 4 (2)Reaction with sulphuric acid. Ethanol reacts with sulphuric acid
C a H 5 .HS0 4 + H.O CjHjOH + H a S0 4 in two distinct ways. If the acid is in considerable excess and the
336 A NEW CERTIFICATE CHEMISTRY ALCOHOLS 337

temperature is about 180°C, the product is the gaseous alkenc, ethy- place the test-tube in a beaker of cold water. Heat it slowly and keep
lene (p. 326). the temperature as high as is possible without allowing the mixture
C a H s OH + H S0 4 -> C 2 H 6 .HS0 4 + H O
2 s in the test-tube to boil. After 20-25 minutes, pour the contents of
C 2 H 6 .HS0 4 -»- C 2H 4 + H 8 S0 4 the test-tube into an evaporating dish about half-full of a concen-
trated common salt solution. Oily drops of liquid should rise to the
With a smaller proportion of the concentrated acid and a lower
surface (the ester, ethyl acetate), having a pleasant smell of pear-
temperature (145°C), the chief product is ether (diethyl ether). This
drops.
is a very volatile, sweet-smelling liquid, formerly much used as an

anaesthetic.
CH .COOH + HOC H
3 2 5 ^ CH 3 .COOC,H 6 +HO a

Notice that the ester formed from the acid by replacing ionisable
C 2 H & OH + H 2 S0 4 ->• C 2 H 5 .HS0 4 + H 2 is

hydrogen (of the COOH group) by the organic ethyl group from the
Then, with excess alcohol available,
ethanol. All the common alcohols produce esters with organic acids
C„H B .HS0 4 + HOC 2 H 5 -»- C H 2 6 .O.C 2 H 8 + H S0 2 4. in this way; the esters usually have a pleasant fruity smell and find
These are both dehydrating actions of sulphuric acid. The severer uses as flavouring materials and in perfumes. The production of a
conditions (excess of the acid and a higher temperature) extract H 2 more complex product like the ester from simpler materials like the
from one molecule of the alcohol. acid and alcohol is called synthesis and is a very frequent organic

C 2 H s OH - H 2 -»- C 2H 4 process.
It can be reversed, to recover the acid and alcohol again, by
Milder conditions (relatively less acid and a lower temperature) hydrolysis, theoretically by water but, in practice, by boiling with
extract H.O between two molecules of the alcohol.
dilute mineral acid (HC1 or HgSOJ or with aqueous caustic alkali as
2C 2 H 6 OH -H 2
0-»- C 2 H 6 .O.C 2 H 6 catalysts. In the acidic case, the products are the alcohol and acid,

(3) Oxidation. Ethanol can be oxidised in two stages. If 1-2 cm 3 of from which the ester is derived.

ethanol are heated with potassium dichromate solution and dilute CH .COOC H + H O ^ CH 3 .COOH + C H OH
3 s 6 s 3 6
sulphuric acid, the liquid turns green (by reduction of the dichromate)
In the alkaline case, the above reaction occurs and is then followed by
and aldehyde is given oiTas a very acrid vapour. the production of the sodium (or potassium) salt of the acid, in this
CH 3 .CH 2 OH -> CHj.CHO + 2H* + 2e~ instance, sodium acetate.
Aldehyde can be further oxidised by more heated potassium dichrom- CH 3 .COOH + NaOH -»• CH 3 .COONa + H 2

ate in dilute sulphuric acid and the product is acetic acid, the acid of The production of soap by boiling a fat or oil with aqueous caustic
vinegar. alkaline hydrolysis of an ester. The ester is the fat or oil, the
soda is

CH .CHO + H
3 2
0-»- CH3.COOH + 2H+ + 2e~ alcohol produced is glycerol and the sodium salt is the soap.

No further oxidation is possible except by combustion of acetic acid Fat or oil + caustic soda —> soap -f- glycerol
vapour to carbon dioxide and water. Because of its oxidation product The chemical formulae are very complex.
(acetic acid), aldehyde is also known as acetaldehyde. Synthesis of terylene. Terylene is a very complex ester (a polyester)
Both these stages of oxidation can also be brought about by passing synthesised from the alcohol, glycol, C 2 H 4 (OH) 2 and lerephtltalic ,

the alcohol or aldehyde, as vapour, with air over a heated catalyst. acid, C eH 4(COOH) 2 These materials condense together when heated,
.

For the first stage, a copper coil is a suitable catalyst. eliminating molecules of water between them. This is exactly similar
CH 3 .CH 2 OH + iO s -»- CH 3 .CHO + H t O in principle to the production of ethyl acetate (above) from acetic

For the second stage, manganese(II) acetate

acid and ethanol, though more complex. The first stage is:
is catalytic.

CH 3 .CHO + ±0 2 -> CH 3 .COOH 2C 2 H 4 (OH) 2 + C,H 4(COOH) 2 -»- C 8 H 4 (C s H 4 2) 2 + 2H,0

(OH) t
The organic product is still an alcohol (notice the two OH groups)
(4) Ester formation. Into a dry test-tube, put about 2 cm 3 of glacial
and can condense with more acid, a process which continues until
it
{i.e., concentrated) acetic acid. Add a few drops of concentrated sul-
the molecular weight of the product, terylene, exceeds 50 000. Tery-
phuric acid (catalyst) and shake. Add 4 cm3 of ethanol, shake and
lene can be extruded as fibres and woven into fabrics, sometimes in
 338 A NEW CERTIFICATE CHEMISTRY
combination with other textiles. It is not a true polymer
(p. 329)
because water is eliminated from the materials as it is
synthesised,
but, because of its complexity, it is known as a polyester.

ACETIC ACID
Acetic acid is the second member of the homologous
series offatty
acids, so called because some members of the series,
e.g., stearic acid,
C 17 H 35 .COOH, can be prepared from fats which are their esters. The
general molecular formula of the acids is
CnH^^.COOH, or
CHOC'S. The first formula is usually preferred because it expresses
the presence of the carboxyl group, COOH, which is the
characteristic
group of the series. The first two members of the series are
formic acid
H.COOH or CH 2 2, and acetic acid, CH .COOH or C a H
3 Notice
4 2.
that, as in all homologous series, successive members have molecular
formula? which differ by CH 2.

Laboratory preparation of acetic acid

Acetic acid is the final oxidation product of ethanol.
The oxidation
occurs in two stages-the first to aldehyde, the second
to acetic acid
Both stages can be carried out in the laboratory by
heating with
chromic acid (i.e., potassium dichromate in dilute
CH 3 .CH 2 OH -
CH 3 .CHO + 2H+ + 2e~
CH3.CHO + H 2 -> CH3.COOH + 2H+ + 2e~
sulphuric acid)

In practice, this method gives a dilute solution

of the acid from which
a pure product is not easily obtained. An
easier preparation is the
distillation of anhydrous sodium acetate
with concentrated sulphuric
acid. Hydrochloric acid is not suitable because
it is volatile and
would
distil with the acetic acid.

CH s .COONa f H 2S0 4 -»- NaHS0 4 + CH 3 .COOH

The apparatus must be all-glass because hot acetic acid
vapour attacks
cork or rubber stoppers. A retort is suitable (see nitric acid p 435)
or a modern glass-jointed distillation apparatus. Acetic
acid distils
as a colourless liquid.

Large-scale production of acetic acid

Pure acetic acid is now made on the large scale
from acetylene
C2H 2 in two stages. In the first stage,
,
acetylene is passed into dilute
sulphunc acid at about 96°C, with mercury(/I)
sulphate present as
catalyst.

C a H 2 + H 2 0-*CH 3 .CHO
The aldehyde vapour produced is then passed over a heated
catalyst
manganeseiJI) acetate, with air as oxidising agent.
CH
a .CHO + ±0 2 -»- CH3.COOH
 '

ACETIC ACID 339

Acetic acid is also manufactured in the form of vinegar, which

contains about 4%
of the acid. A
dilute aqueous solution of ethanol,
e.g., a wine of poor quality, is run slowly over coke in a well-aerated
vat. The coke is smeared with 'mother of vinegar', a white solid
material containing the bacterium, mycoderma aceti. This acts as a
catalyst to oxidation of ethanol by oxygen of the air. The liquid may
have to pass through the vat several times to secure full oxidation.
CHa-CHgOH + 2 ->CH 3 .COOH + H 2

Properties and reactions of acetic acid

Physical properties. In English conditions, acetic acid is usually a
colourless liquid with a strong, very irritating smell. It mixes with
water in all proportions and a dilute solution has the usual sour taste
of an acid. The melting-point of the acid (17°C) is near room tem-
perature. In winter, the pure acid may freeze to crystals resembling
ice; hence the name glacial acetic acid which is usually used for the
pure material.
Chemical reactions. (1) Acidic behaviour. Acetic acid is a weak acid,
that is, it is slightly ionised in dilute solution. For example, at 0.1M,
or 6 g/dm3 , the acid has a degree of dissociation of 1.4%; at M, it is
0.4%.

Imperial Chemical Industries U4.

CH3.COOH ^ CH3.COO- + H +
P.- ate 8. (a) Top section of .he la.es. Oslo evaporator for
making granular salt, in .he
The presence of H + gives the solution the usual acidic behaviour, as
I.C I Works
at Slokc. below.
PLA It turns blue litmus to red.
( h)An opcn he:,r [h furnace being charged with raw material
*JL
shown : .
has a capac.ty ofr .53 tons, taking
.
for steel-makinc The funwt It forms a salt with an alkali or base.
about nine hours for melting and relining 'he charg.T
L^ a^^^^^^^^^—^^—^—,-,. Slemirl\ u-ul I /nl'ilt Ltd.
CH3.COO- + H + + Na+ + OH--> CH 3 .COO-Na+ +HO s

It liberates carbon dioxide from a carbonate or bicarbonate.

CO sa - + 2H+ -> H 2 + C0 2
HCO3- + H+ ->- H 2 + C0 2

It liberates hydrogen on contact with a strongly electropositive

metal, e.g., Mg.
Mg + 2H+ ->• Mg2+ + H 2

All compounds containing the carboxyl group, COOH, show these

weakly acidic reactions. This includes all the fatty acids and also
compounds which do not belong to this series, e.g., oxalic acid and
tartaric acid. These are both dicarboxylic acids, containing two car-
boxyl groups per molecule.
Oxalic acid Tartaric acid
HC 8 2 4 or (COOH) 2 C 2 H 4 O s (COOH) 2
Both acids can neutralise alkali in two stages, giving an acid salt and
 340 A NEW CERTIFICATE CHEMISTRY CHROMATOGRAPHY 341

a normal salt. For oxalic acid with sodium hydroxide solution, the alanine, CH 3 .CH(NH ).COOH. This occurs because the protein
2
stages are: -CO.NH—
and they break down in
+ NaOH - NaHC,0 4 + H,0
contains peptide linkages, ,

HC 2 2 4 hydrolysis by using the elements of a molecule of water.

H C2
2 4 + 2NaOH -> Na C 2 2 4 + 2H 2 -CO.NH— + H O->- —COOH + NH — s 2
The other acidic properties given for acetic acid are also shown by
these acids, but the liberation of hydrogen with metal may be negligible
The COOH and NH groups are then constituents of different amino-
2

acids. Quite complex mixtures of aminoacids and other organic

for very weak organic acids.
mixtures of compounds can now be investigated very efficiently by
(2) Ester formation. A mixture of glacial acetic acid and moderate the technique of chromatography, about which something will be
excess of a simple alcohol, e.g., CH 3 OH or C„H OH, boiled unders written in the next section of this chapter.
reflux with a little concentrated sulphuric acid or dry hydrogen chlor-
Complex compounds closely resembling natural proteins can be
ide present as catalyst, produces an ester. For example, with ethanol
built up in the laboratory by condensing aminoacids together, i.e.,
CH 3 .COOH + C H OH ^ CH 8 .COOC H + H
2 6 2 6 2 causing them to combine by eliminating water molecules between the
For more details, see p. 336. NH S group
of one aminoacid and the COOH group of another. This
(3)With chlorides ofphosphorus. Glacial acetic acid reacts rapidly forms a peptide linkage in the course of creating a more complex
in the cold with phosphorus pentachloride. 'Steamy' fumes molecule.
of
hydrogen chloride are given off and the organic product is acetyl R.COOH + NH 2 .R, -> R.CO.NH.R, + H 2
chloride, a colourless liquid which fumes in air.
R and tKrepresent the rest of the aminoacid molecules. The con-
CH s .COOH + PCI 6 -»- CH 3 .COCl + HC1 + POC1, densation can be continued to give a quite large, protein-like mole-
This reaction shows the presence of the hydroxyl group, cule, but with nothing like the complexity of a natural protein so far.
OH, in the
acid; it is part of the carboxyl group, COOH.
Chromatography
Phosphorus trichloride reacts similarly but more slowly: slight
heating is required. Chromatography is a means of separating the constituents (usually
organic) of a mixture by taking advantage of their different rates of
3CH s .COOH + 2PCI 3 ->- 3CH 3 .COCl + P O s + 3HC1 2 movement (in a solvent) over an absorbent medium. For each con-
Notice that the chlorides of phosphorus attack the group of COOH stituent, the rate of movement depends on the relative affinities of
the acid but leave the CH 3 group unchanged. the constituent for the solvent and the absorbent medium. In paper
(4) With chlorine. If glacial acetic acid is boiled under reflux while chromatography, which is one of its most useful forms, the absorbent
chlorine is passed in, monochloroacetic acid is produced. Light medium is filter-paper and a variety of solvents can be used, e.g.,
catalyses this reaction (photocatalysis). ethyl acetate, methanol, aqueous phenol. The following experiment
Cl 9 + CH3.COOH - CH,Cl.COOH + HC1 illustrates the process of chromatography in a simple way. A pin-
cm
Further passage of chlorine will give, in succession, di-
hole is made at the centre of a Whatman No. 1 filter-paper of 12.5
and trichloro-
cm
acetic acid, CHCl 2 .COOH and CCl 3 .COOH respectively. diameter. String is threaded through the hole and cut to 0.5
Notice that
CH length on one side and 5 cm on the other. A drop of BDH
universal
chlorine attacks only the group, leaving the 3 group intact. COOH indicator is then placed in the centre of the filter-paper and allowed
If monochloroacetic acid is allowed to react with aqueous
am- and turn brown A Petri dish (or shallow crystallising
monia, it is converted to aminoacetic acid, also called glycine. to dry out in air.
t is NH dish) of 10 cm diameter is about one-third filled with the solvent,
called the amino group.
ethyl acetate, and the filter-paper so that the longer
is placed over it
2NH 3 + CH 2 Cl.COOH -> CH a NH 2 .COOH + NH 4 C1 end of string dips into the solvent. Another, similar dish is placed on
Excess of ammonia would produce the ammonium salt of glycine top (Fig. 1 1 1), to make a closed system. Ethyl acetate will ascend the
CH NH .COONH 4
2 2 . string and spread over the filter-paper so developing a chromatogram
Glycine and other, more complex, aminoacids are very important of the constituents of the indicator. That is, after a suitable time (up
biological materials. For example, a protein, boiled with dilute acid, to an hour), bands of the different dyes present will be seen— a purple
e.g., H 2S0 4 is hydrolysed into aminoacids, such as glycine
,
and colour ahead, a yellow colour about halfway and a red-brown dye
 342 A NEW CERTIFICATE CHEMISTRY AMINES 343
remaining close to the centre. If methanol is the solvent, an A
outer To secure better separations, the following device may be used.
yellow band occurs, with an inner red band and no residue
at the square piece of filter-paper is employed and a chromatogram is
centre.
developed from a spot of material near one corner of the paper. This
In standard chromatography, rectangles of filter-paper above. The paper
about 22 gives spots of separated materials along a line, as
cm by 5 cm are usually used. A
spot of solution containing the chromatogram developed by using the
is then dried and a second is
mixture under investigation is placed near the middle of one
of the same piece of paper at right angles to its former position and with a
short ends of the filter-paper and about 3 cm away from
the end. different solvent.Spots of material will then be found, after drying,
Then the spot is allowed to dry. The paper is then suspended verti-
much more widely spread over most of the surface of the paper.
cally with the spotted end immersed in the solvent
but the spot well
clear of the liquid level. The whole is enclosed
by a covering vessel
to prevent loss of solvent. The chromatogram will then develop
as the
solvent rises up the filter-paper. Spots of the various constituents
AMINES
of
Amines are members of the homologous series which has a general
Dried spot of indicator (BDH universal) molecular formula of C„H M , ,NH 2 for its constituents. The first
two
conditions) are methylamine,
members (both gases in ordinary
NH NH
CH 3 2 , and ethylamine, C a H 6 2 The amino group, . 2 is the NH ,

characteristic group of all members of the series. Like all

such amines,
Petri dish
{or similar) thesetwo compounds are derived from ammonia by replacing one
hydrogen atom of the NH 3 molecule by an organic group such as
CH S or CjH 8 .

H C2H5
H—N-H H—N-H or C H NH 2 6 2
ammonia ethylamine

ethyl acetate Properties of simple amines. Methylamine and ethylamine are

(or other solvent) colourless gases at room temperature and pressure; they have a
are very
Fio. 111. strong smell of fish and ammonia and, like ammonia,
A simple example of chromatography. soluble in cold water. They burn in air and this distinguishes them
from ammonia, which does not.
the original mixture will collect, at different
distances along a verti-
cal line, above the original spot. When the
ascending front of solvent Basic nature of amines
is approaching the top of the
paper (usually eight hours or more Like ammonia, the amines given an alkaline reaction in aqueous
after the start), the paper is removed and
dried. It can then be ex-
solution by producing a considerable concentration of hydroxide
amined in various ways to locate the spots of material
left and to ion, OH-.
identify their contents.
For example, the paper may be examined in ultra-violet C 2 H 6 NH 2 + H 2 ^ C 2 H NH S + + OH"
B

which may cause fluorescence and so indicate the position

radiation,
Compare NH 3 + HsO «* NH, + + OH"
of some
compounds; or the paper may be sprayed with a reagent giving
colour Both methylamine and ethylamine turn damp red litmus paper blue
reactions with compounds present. If desired, areas of paper on and are, in fact, stronger bases than ammonia at corresponding
which spots of materials have been detected may dilutions.
be cut out and
'eluted' with a solvent, so providing a solution Just as ammonia forms with mineral acids, the amines pro-
salts
in which a compound
may be identified by the usual methods of micro-analysis. Two duce corresponding salts, which can be obtained as similar white
of the
advantages of chromatography are that it can be performed crystals.
with very
small weights of material and they are not destroyed in
the process. C 2H 6 NH, + HC1 -> C,H 5 NH 3 + C1- (ethylamine chloride)
344 A NEW CERTIFICATE CHEMISTRY POLYSTYRENE 345

Compare variety of attractive garments (underwear, stockings, shirts) and into

NH + HC1 -»• NH/C1- (ammonium chloride) tow ropes, tyre-cord, nets and racquet strings, which require strength
S
and durability. Nylon powder can be moulded, while hot, into
These amine salts liberate the free amine when warmed with aqueous
various plastic articles, e.g., gears and bearings in small machines
caustic alkali, just as an ammonium salt liberates ammonia in the
such as electric mixers and razors, where toughness is required.
same conditions.
(The actual compounds used in making nylon, both petroleum
QH 5NH 3 +C1- + Na + OH- -»- Na + Cl" + H aO + C,H NH S 3 derivatives, are:
Compare HO— CO(CH ),CO-OH 3 and H—NH(CH NH— 2) 8
NH«+C1- + Na+OH- -» Na+Cl" + H,0 + NH8 adipic acid hcxamethylcncdiamine

Like aqueous ammonia, a solution of a simple amine supplies a large From this, X is -CO(CH 3) 4 CO— and Y is — NH(CH,),NH— and
enough concentration of hydroxide ion to precipitate the insoluble the linear nylon molecule is:

hydroxides of several metals from solutions of their salts, e.g., iron(lll),

. . . —CO(CH g
)«CO— NH(CH 2 ) 8 NH—CO(CH 1) 1—
zinc and aluminium hydroxides. CO— NH(CH )„NH- . .

Fe 8+ -
+ 30H- Fe(OH) 8
+ + 20H- -»- Zn(OH),
(Al similar) Notice the peptide linkages, — CO— NH—
, in this chain. It is found
2

Zn 2 that, in 'condensation polymers' like nylon, the total number of

CH 3 groups in the two constituents must be at least eight, and pre-
Preparation of an amine ferably nine. Otherwise, cyclic compounds of small molecular
weight will form, not very large linear molecules as in nylon.) Two
Ethylaminc can be prepared by the reaction between ethyl iodide
other important linear polymers are the following.
(a liquid) and concentrated aqueous ammonia. Heating at 100°C in
a sealed tube is required.
Polystyrene
C.H.I + 2NH 3 ->- C 3H 5 NH a + NH 4I
Styrene is phenyl ethylene, C„H 6 .CH=CH 3 . It is a colourless liquid
By-products are also produced and the isolation of the amine is prepared (in two stages) from benzene, C B H„, and ethylene. It poly-
difficult. Methylamine can be prepared by a corresponding method
merises slowly at ordinary temperature and rapidly if heated to
from methyl iodide, CH 3 1. 100-150°C, preferably in nitrogen, to prevent oxidation. It produces
polymers of average molecular weight about 120 000 at 100°C and
Nylon about 23 000 at 150°C. The polymers have a linear structure resembl-
Nylon is usually called a superpolymer though it is not a true poly- ing that of polythene (p. 329), but with a phenyl (C 8 H 5 ) group attached
mer (p. 329) because water is split out between pairs of molecules as it to each alternate carbon atom.
forms. These molecules are of the types HO— X — OH and H — Y—
and the essential reaction is: — CH —CH—CH,—CH—CH,—CH—CH -CH—CH -CH—
t 3 a

C.H. C.H 5 C aH B C 8H 5 C8H

. .
.-|H+ HOI— X^OH + Hr-Y-JH + HOl-X— 6

OH + H-Y— H + HO—X— OH + H — ... The polymer is a white solid and can be depolymerised (back to
styrene) at about 350°C.
—X—Y—X—Y—X—Y—X—Y— + mH,0 Polystyrene is a very good electrical insulator (especially for high-

This produces a greatly extended linear molecule which is nylon.
The process is done in two stages, the second with heat and pressure
in an autoclave and, after cooling, the nylon appears as chips. By
melting the chips and forcing the liquid through tiny holes in a metal
disc (a spinneret), filaments are formed, stretched between rollers
and then gathered into nylon yarn. This yarn can be woven into a
frequency work) and, being water-resistant, can be moulded into
battery casesand refrigerator parts. Expanded polystyrene (in the
form of blocks and mouldings) can be used in thermal insulation
and also in packaging and display. Great quantities of styrene
(25%) are co-polymerised with butadiene (75%) in making a
synthetic rubber.
 C :

346 A NEW CERTIFICATE CHEMISTRY QUESTIONS 347

Perspex (methyl methacrylate polymer) 5. Show, by equations and brief comment, the chemical relation between

An ethanol and acetic acid. How, and in what conditions, does acetic acid
acidic derivative of ethylene is acrylic acid, CH s=CH.COOH. react with (a) chlorine; (b) phosphorus pentachloridc ? Describe briefly the
Methylacrylic acid is CIV=C(CH 3).COOH
its methyl ester is and preparation (without purification) of one ester of acetic acid. How
does
CH =C(CH ).COOCH 3
s 3 This ester, methyl methacrylate, having a
. this ester behave if boiled with aqueous
sodium hydroxide?
double bond like ethylene, polymerises in a corresponding way. The 6. Explain why acetic acid shows 'acidic' reactions and state two such
polymerisation is carried out at 80-90°C in an emulsion of the ester reactions (other than behaviour with litmus). In what way, and why, does
in dilute aqueous soap solution with hydrogen peroxide present. the acidity of this acid differ from that of hydrochloric acid ? State (a) in
outline a good method for the preparation in the laboratory of reasonably
After cooling, the mixture is poured into very dilute hydrochloric
pure acetic acid; (b) the chemistry of one large-scale method of making
acid when the polymer coagulates and is separated, washed and acetic acid.
dried. The polymer is linear, like polythene, but has CH 3 and 7. Explain the basic nature of ethylamine, C,H 6 NH„
and compare the
COOCH 3 groups attached to alternate carbon atoms. behaviour of this compound with that of ammonia towards hydrochloric
acid. How, by one chemical test, would you distinguish ethylamine from
CH, CH 3 CH S CH S CH S ammonia (both gaseous)? If ethylamine is the second member, write the
molecular formula of the fifth member of the homologous series. Mention
I2—C—CH, two differences of physical properties you would expect between the two
compounds.
I
COOCH3 COOCH
COOCH,3 COOCH 3 COOCH 3 COOCH
C< 8
8. How, by one chemical test in each case, would you distinguish between
(a) ethane and ethylene; (b) ethanol and acetic acid; (c) ethylene and acety-
The polymer is colourless and transparent. When softened by heat, lene? Outline one conversion of ethylene into ethanol.
it can be moulded into objects with optical uses, e.g., lenses and 9. Explain what is meant by polymerisation. Outline the manufacture
reflectors, and, in sheet form, as 'Perspex' can replace the much of polythene. Write a short account of its uses and why it is suited to them.
denser glass in aeroplane domes and windows. It is also moulded Explain why terylene is called a polyester. Why is it not a true polymer?
into artificial dentures and small household articles. (Notice how, in What is the chief use of terylene in ordinary life?

both polystyrene and the methyl methacrylate polymer, the double 10.There are two isomers of molecular formula, C,H»0, i.e., an alcohol
and a compound of another type. Write their full structural formula;.
bonds of the simple compound are lost and the polymer is a saturated Give one chemical test to distinguish between them. Write full structural
material.) H
formula; for the two isomers of butane, C4 10 Pentane,. QH,,, has three
isomers. Write full structural formula: for two of them.

QUESTIONS
1. What
is meant by the term hydrocarbon! Give the molecular
formula
of one gaseous alkane and one gaseous alkene hydrocarbon.
Contrast
the reactions of these two with chlorine. Give one good test
by which the
two gases may be distinguished and explain it.

State briefly without diagrams how ethylene and acetylene are

2.
pre-
pared and collected in the laboratory, mentioning suitable conditions
of
reaction. Contrast the behaviour of these gases with pure chlorine.
Give
the chemistry of the large-scale preparation of one important
product from
each of these hydrocarbons and mention how the product is used in each
case.
3. QHjOH is the molecular formula of the second member of the
homologous series of alcohols. Write the molecular formula of the fourth
member. Mention two differences of physical properties which you would
expect the two compounds to show. Give two examples of similarity
of
chemical behaviour you would expect from these compounds.
4. What is a peptide linkage? How does a peptide linkage
of a protein
behave when the protein is hydrolysed? What are the resulting products?
Explain what value paper chromatography has in investigating
reactions
of this kind and state, in outline, how the experimental work is carried
out
 SILICON 349

and retire to a distance of two metres or more. After a few moments

the reaction occurs with a flash of light. Allow to cool, break the
test-tube in a mortar and pick out the pieces of brown amorphous
silicon.
2Mg + Si0 2 -»• 2MgO + Si
Chapter 25
Reactions of silicon
Place a small piece of silicon, obtained in the above experiment, on
a tripod stand and direct the flame of a Bunsen burner on to it from
Silicon and its Compounds above. It will react, sometimes by burning, to form a white solid,
(For silicon in periodicity, see silica.
p. 87)
Si + 2 -*-SiO»
Put the rest of the silicon into a test-tube, add sodium hydroxide
SILICON is the second most abundant element in the earth's crust, solution and warm. There is an evolution of hydrogen and finally the
the most abundant of all being oxygen. Silicon is found in the silicon dissolves.
following forms: -> Na 2SiO s + 2H 2
2NaOH + Si +H 2
1. As
metallic silicates. Igneous rocks, such as granite and basalt,
Amorphous silicon combines with chlorine at low red heat and
consist largely of mixtures of silicates, those of magnesium, alu-
minium, potassium and iron being most common. China clay, kaolin, also decomposes steam.
is a hydrated silicate of aluminium; ordinary clay is a mixture of Si(c) + 2Cl (g)->SiCl,(l)
2

particles of quartz, mica and other substances bound together by a Si(c) + 2H 20(g)-»- Si0 (c) + 2
2H 2 (g)
sticky material which is a hydrated silicate of aluminium of approx- Silicon is used in the manufacture of certain types of steel and
imate formula Al 2 Si 2 7 .2H aO. bronze.
2. As silica {silicon dioxide), SiO t The purest form of silica is rock
.

crystal or transparent quartz. Sand usually consists of silica, with SILICON DIOXIDE (SILICA), SiO,
various impurities, and opal, hornstone and jasper are forms of this
Silica from sodium silicate
oxide. It also exists in a less pure form as flint.
The porous material 'kieselguhr', is a form of silica made up of the Add concentrated hydrochloric acid to a solution of sodium silicate
fossil shellsof small plants called diatoms. It is used to absorb the and warm if necessary. White hydrated silica (silicic acid) will come

explosive, 'nitroglycerine', forming the product called 'dynamite', down as a gelatinous precipitate.
which is safer to transport and handle than the explosive itself. Na 2SiO s + 2HC1 -»- 2NaCl + Si0 2 .H aO
Show that the precipitate is readily soluble in dilute caustic soda
SILICON solution.

The element may be prepared in the amorphous state by heating 2NaOH + SiO a
-»- Na 2SiO s + H2
magnesium powder with silica, SiO a .

Uses and properties

SiO a + 2Mg->2MgO + Si
In its naturally occurring form, sand, silica finds great use as a
The reaction is very violent.
constituent of mortar and cement, for the manufacture of glass (see
Silicon from silica p. 352) and for filtration of water in bulk.
Fused silica is used for the manufacture of certain types of labora-
Mix one 'saltspoonful' of magnesium powder with three times its is very low (about one-
tory apparatus. Its coefficient of expansion
bulk of amorphous silica and place the mixture in a test-tube.
fiftiethof that of glass) and consequently the strains set up in it
Clamp the tube with the mouth pointing upwards and in a safe direc-
by irregular contraction under sudden reduction of temperature are
tion, place a Bunsen burner underneath the tube to heat it
stronelv small and insufficient to break it. A red-hot silica tube or crucible
348
 350 A NEW CERTIFICATE CHEMISTRY SILICA 351

can be plunged into cold water without damage. Fused quartz ortho-silicic acid, is obtained by the action of water on silicon
threads are used in the construction of physical apparatus. They can tetrachloride.
be made so thin as to be invisible to the naked eye and yet strong
enough to support a weight of 2 g. Their tenuity and elasticity
Na 2 Si0 3 + 2HC1 -* H 2 SiO„ + 2NaCl
SiCl 4 + 4H s O -> H 4 Si0 4 + 4HC1
make them invaluable for light, delicate suspensions. The difficulty
working fused silica The salts of these acids are called silicates. The meta-silicates are the
in is that the very high temperature of at least

1500°C is required. most important.

Silicon dioxide (silica) is almost insoluble in water. It acts as the
Sodium silicate (water-glass), Na aSK) 3
acidic oxide of a non-metal and forms silicates with caustic alkalis
and metallic oxides Sodium silicate is prepared by heating two parts by weight of silica
(all heated).
with one part of sodium carbonate.
SiO, -f 20H- -> SiO s *- + H t O or SiO, + 0«- -»- Si0 2-

Silicon dioxide forms three-dimensional crystalline systems

3
Na 2 C0 3 + SiO,-* NaaSi0 + CO, 3
of great
The product is a glassy heated with water (under pres-
solid. It is
complexity. In simplest form (cristobalite), the silicon atoms are
its
arranged carbon atoms of diamond (p. 288) but with oxygen
like the sure) to dissolve it, and is sold in tins in the form of a concentrated
atoms midway between them. This macro formation accounts for solution, similar in consistency to 'golden syrup', but colourless.
the high melting point of silica in contrast with the gaseous state of This is called 'water-glass'.
carbon dioxide at s.t.p. This gas contains only separate molecules of Water-glass is chiefly used for preserving eggs. The shell of an egg
carbon dioxide (p. 73). consists largely of calcium carbonate. This, when the egg is im-
mersed in a suitable solution of 'water-glass', reacts with the sodium
Sodium silicate from silica
silicate to produce a precipitate of calcium silicate which seals the
Wash some of the white gelatinous precipitate of hydrated silica pores of the shell, excluding bacteria and so preserving the egg from
obtained above and ignite it in a crucible. The product is amorphous putrefaction.
silica and is no longer easily soluble in caustic soda solution even
if CaCOg + Na,Si0 8 -* CaSiO„ + Na C0 88
hot and concentrated. That silica is an acidic oxide can, however, be
shown as follows: Put a small piece of solid sodium hydroxide about Silica-garden
half an inch long into a crucible, add a 'saltspoonfuP of amorphous can
An interesting chemical phenomenon, called a 'silica-garden',
silica and heat the mass strongly for about ten minutes. Take
great be shown the following way. Dilute some water-glass until it has a
in
care when doing this, that none of the molten mass is spilled or comes
density of 1.1 g/cm 3 (test with a hydrometer), then filter it and put
into contact with the flesh. Allow the melt to cool, fill the crucible
the liquid into a tall, rather narrow vessel. Drop into it crystals of
two-thirds full of water and warm. The solution obtained is sodium
manganese(II) chloride, cobalt nitrate, iron(II) sulphate and
silicate and from it gelatinous silica can be obtained by the action of
copper(II) sulphate. From these crystals there will shoot fantastic
hydrochloric acid.
coloured growths. Those from the cobalt salt usually appear within
Silica is non-volatile and can, at high temperatures, displace
a few seconds and grow rapidly. They are dark blue. Growths from the
volatile acidic oxides from combination. They pass off as vapour,
other crystals appear more slowly. Those from the manganese salt
leaving a silicate, e.g.,
arc pale pink, from copper sulphate light blue, and from the iron(II)
Na,S0 4 + Si0 2 -»- Na 2 Si0 3 I SO a salt green. The growths are tubes of the silicates of the metals.

Silicates
Silica gel
Silicates are salts of the silicic acids. The chemistry of these acids
is added to a concentrated solution of sodium
If hydrochloric acid
is complex, and little is known for certain
about them.
silicate at about 100°C, a product known as silica gel is precipitated.
The gelatinous substance precipitated by acidifying a hot solution
It contains 5-7% of water and is regarded as a partially hydrated
of 'water-glass' has the empirical formula H 2 Si0 3 , and is called
silica.
meta-silicic acid, and an acid of approximate formula H SiO«,
4 Na 8Si0 3 + 2HC1-* 2NaCl + SiQ 2 .H 2
352 A NEW CERTIFICATE CHEMISTRY
Silica gel absorbs water-vapour very readily and is used for drying
gases on the industrial scale, e.g., in drying air for the blast of a blast-
furnace. When spent, the gel can be re-activated by heating to a suit-
able temperature.
can also absorb volatile solvents, e.g., carbon disulphide
Silica gel
or acetone, which would otherwise be lost as effluent. The solvents
can be recovered by suitable heating of the gel. It has also been used
successfully for freeing petroleum oils from sulphur compounds.
SILICON TBTRACHLORIDB 353
softening of glass before it melts is a very valuable property.
The
Itenables a skilled worker or a machine to blow it into various
shapes— bottles, flasks, beakers— by using suitable moulds. While
soft, glass can also be moulded and joined to produce elaborate
scientific apparatus. Large sheets of glass are produced by rolling
out a mass of hot glass on a long, flat table or by floating glass on
molten tin while heating the top surface. Glass-tubing is made by
first blowing a mass of glass into a thick-walled cylinder, and then

drawing the cylinder out between two workers walking in opposite

Glass
directions, one manipulating the blow-iron. The 'unbreakable glass'
The substance to which the term 'glass' is usually applied consists used for motor-car windscreens is made by cementing a sheet of glass
of a mixture of two or more silicates. Common soft glass, of which
on to each side of a sheet of celluloid. The cement prevents splinters
bottles and laboratory apparatus are made, is prepared by heating
from flying off.
together silica in sodium carbonate or sodium
the form of sand, Articles of glass usually have to be annealed, that is, heated
made
sulphate, and chalk or limestone (calcium carbonate). (Some broken and then allowed to cool very slowly and
to a suitable temperature
glass and a little coke are usually added.) The glass so prepared con-
uniformly so that no stresses are set up which might break the glass.
sists of a mixture of sodium silicate and calcium silicate.
The annealing of considerable masses of glass may require several
NajCOg + SiQ 2
-*- Na 2 Si0 3 + C0 2 weeks, or even months, as in the case of the glass for the mirror of
or or the 500 cm telescope erected at the Mount Wilson observatory in the
U.S.A. Working with glass is a very ancient art. It was practised by
Na 2SO« S0 3
the Egyptians at least 2300 years ago, while some of the finest speci-
CaC0 3 -f SiO a -»- CaSiOa + C0 2
mens of glassware are the work of Venetian craftsmen of the Middle
If potassium carbonate used instead of sodium carbonate, a
is
Ages.
'hard' glass, that is, a glass needing a higher temperature to melt it,
will be produced, and will consist of a mixture of calcium silicate and Silicon tetrachloride
potassium silicate. combines with chlorine when heated to form silicon tetra-
Silicon
Glass containing lead silicate has a brilliant appearance, and is chloride, but a more convenient method of producing this compound
made by adding to the ordinary glass mixture some red lead, Pb s 4 , (because it does not require the element, silicon) is to heat an intimate
or litharge, PbO. Such a glass ('flint glass') has a high refractive index mixture of silica and carbon in a current of dry chlorine.
and is used for prisms and lenses, but it is soft and should be wiped
only with silk, to avoid scratching the surface.
SiO, + 2C + 2C1 2
- SiCl< + 2CO
vapour and can be condensed to a
Silicon tetrachloride distils off as
Coloured glass is obtained by addition of metallic oxides, for
colourless liquid of boiling-point 58°C at 760 mm. It may contain a
example, cobalt produces blue glass, chromium produces green glass.
small proportion of other chlorides, e.g., Si 2 Cl e .
Opalescent glass may be produced by addition of calcium phosphate.
Properties
Physical nature of glass
(1) Silicon tetrachloride reacts rapidly with cold water, forming
Glass not really a solid. This is shown by the fact that, when
is hydrogen chloride and silicic acid.
heated, it does not suddenly pass from the solid to the liquid state at -* 4HC1 + H 2 SiO a
SiCl, + 3H 2
a definite temperature, but softens slowly as the temperature rises
This reaction (with atmospheric moisture) causes the tetrachloride to
and gradually becomes liquid. A true solid would melt suddenly over
fume in moist air. Carbon tetrachloride, CC1 4 however, has no ,

a small temperature range. Glass is a super-cooled liquid. By this we

reaction with water, which is unusual for the chloride of a non-metal.
mean that its molecules have not taken up a definite formation to
(2) If heated with an alkali-metal, silicon tetrachloride is decom-
produce crystals, but are arranged at random as they were in liquid
posed to form silicon.
glass.
SiCl« + 4K -»• Si + 4KC1
354 A NEW CERTIFICATE CHEMISTRY

QUESTIONS
1. What is the chemical nature of glass? How is it made? Why is glass
stated to be a super-cooled liquid?
2. Silica is an acid-forming oxide. Justify this statement by reference to
Chapter 26
the chemical properties of silica.
3. In what forms docs silica occur in nature? How may the element
silicon be obtained from silica?
4. What is silica? Starting with the naturally occurring substance Chlorine
describe how you would obtain (a) water-glass; (Z>) a solution of silicic acid
and (c) pure silica. (L.)

5. Describe in outline two methods by which silicon may be prepared

fluorine, chlorine, bromine and iodine,
in the laboratory from silica, SiO,. How, and in what conditions, does
silicon react with (a) sodium hydroxide, (6) chlorine, (c) oxygen? Compare
THE four non-metals,
make up a family of related elements, the chemical properties of
the behaviour of carbon with that of silicon towards these three reagents. which form an interesting study. The first of the series is the very
Describe a laboratory preparation of a concentrated solution of active that it evaded efforts to
6.
active element fluorine, which is so
sodium silicate from silica, SiOt How may the product silica gelbe obtained
.
many years, because it reacted with almost every element
isolate it for
from this solution? Briefly discuss the large-scale uses of this product.
or substance with which it came into contact—even the glass of the
7. Describe in brief outline a preparation of silicon tetrachloride from
apparatus in which the reaction took place! Of fluorine we need say
silica, SiOj. Compare and contrast the elements carbon and silicon with
reference to the chemical nature of their dioxides and the behaviour of but littlesince so difficult to isolate that its properties could have
it is

their tetrachlorides with water. Mention the experimental evidence for your no practical application in the school laboratory, and of the others
statements. 'arithmetical mean' between
we shall see that bromine is almost an
in 1774.
chlorine and iodine. Chlorine was first isolated by Schcele
Scheele was a Swedish apothecary' who carried out, during
the
years of age), a vast
short time which he lived (he died when only 44
number of illuminating experiments, performed in an old shed
properties
attached to his house. It was whilst he was investigating the
con-
of pyrolusite (impure manganese dioxide) that he heated it with
chlorine
centrated hydrochloric acid in a retort and collected the
gas which came off into a pig's bladder.
It is usually made by the oxidation of
concentrated hydrochloric
acid. The oxidation can be brought about by many oxidising agents,
manganese dioxide, red lead or potassium
for example, lead dioxide,
permanganate.
H:C1
o+
,
i H sO + Cl g
H:C1
oxygen from concentrated water chlorine
oxidising agent hydrochloric
acid

acid by oxi-
Preparation of chlorine from concentrated hydrochloric
dation with manganese dioxide (manganese(IV) oxide)

Fit up the apparatus as shown in Fig. 112.

Put some manganese
acid down the
dioxide into the flask, pour concentrated hydrochloric
355
 356 A NEW CERTIFICATE CHEMISTRY CHLORINE 357

funnel and shake well before connecting up the flask with the rest of atonce the corresponding quantity of chlorine. The apparatus is filled
the apparatus. (Note. The use of a gas-ring and gauze keeps
the with the greenish-yellow fumes of the gas. Several gas-jars of the gas
flask low and makes the apparatus more stable.) should be collected and the experiments described later performed to
Heat the mixture in the flask and effervescence is observed. A illustrate its properties.
greenish-yellow gas is evolved which, together with a certain amount
of hydrogen chloride (misty fumes), passes over into the Concentrated
first bottle '
Hydrochloric
acid

Chlorine

Fig. 113.
Preparation of chlorine.
Water to remove *Conc Sulphuric
Hydrogen Chloride acid to dry the. gas
Preparation of chlorine from common salt (sodium chloride)
Fio. 112.
Preparation of chlorine. Chemistry of the action. Concentrated sulphuric acid acts upon
the sodium chloride to form hydrogen chloride, which is then oxi-
which contains water. This removes the hydrochloric acid gas (which dised to chlorine by manganese dioxide.
is very soluble in water), and the concentrated sulphuric acid in the The apparatus is identical with Fig. 112, and the experiment is

second bottle dries the gas which is collected by downward delivery, performed in a similar manner except that an intimate mixture of
the gas being denser than air. sodium chloride and manganese dioxide is placed in the flask and con-
MnO,(c) + 4HCl(aq) - MnCl, + 2H,0 + Cl*(g)
centrated sulphuric acid added. In this experiment the presence of
hydrogen chloride as an impurity is more obvious. It is removed by
The above experiment should be
carried out in a fume-chamber, as
passing the gases through water, and the chlorine is dried by means
should any preparation of chlorine in which it is collected by dis-
placement of of concentrated sulphuric acid and collected as shown in Fig. 112.
air.
2NaCl + MnO t + 2H S S0 4 -* Na 8 SO« + MnS0 4
Preparation of chlorine from concentrated common manganese concentrated sodium manganese
hydrochloric acid by sulphate
salt(sodium dioxide sulphuric sulphate
oxidation with potassium permanganate
chloride) mangancsc(IV) acid
[If the chlorine is required pure and dry, insert wash-bottles containing oxide + 2H 2
-+- Cl t
(a) water, and (6) concentrated sulphuric acid in Fig. 113 and collect by water chlorine
displacement of air.]
2KMnO t + -> 2KC1 Preparation of chlorine from bleaching powder
16HC1 + 2MnCl, + 8H O + 5C1
s 8
This a very convenient laboratory method because it takes place
is In this case the chlorine is not prepared by the oxidation of con-
in the cold, and, if the gas is collected over brine, the experiment centrated hydrochloric acid. The apparatus used is identical with
need
not be conducted in a fume-chamber. Fig. 113 (above), bleaching powder is placed in the flask and a
is dropped on to the powder. Efferves-
dilute acid, e.g., nitric acid,
Solid potassium permanganate is placed in a flask and concen-
trated hydrochloric acid is dropped on to it from a tap-funnel (Fig. cence occurs and the greenish-yellow gas can be collected by either
113). As each drop of acid reaches the permanganate, there is evolved of the methods mentioned previously. Heat is not required.

X
 358 A NEW CERTIFICATE CHEMISTRY PROPERTIES OF CHLORINE 359
CaOCl 2 + 2HN0 3 Ca(N0 3 ), + H,0 + CI 2
-
is a very reactive compound and readily
This hypochlorous acid
•

bleaching dilute calcium

powder
water chlorine
gives up its oxygen to the dye, to form a colourless compound,
nitric acid nitrate
Similarly: dye +
HOC1 -»- HC1 (dye -I- O) +
coloured colourless
CaOCl, + 2HC1 -+ CaCl + H,0 + 2 CI, Notice that hydrochloric acid is produced whenever chlorine
dilute
hydrochloric acid bleaches, and hence an article must be thoroughly washed after
bleaching or it will be attacked by the free acid.
CaOCl, + H^O,-*- CaSO« + H 2 + CI,
dilute In industry, the article to be bleached is dipped into a tank con-
sulphuric acid taining bleaching powder in water, then into very dilute sulphuric
acid. It is then washed by water to remove acid and
may be treated
Industrial preparation
with an anti-chlor to remove remaining chlorine, which, if left, might
By electrolysis of brine (see p. 253). A typical anti-chlor is sodium thiosulphate ('hypo'),
rot the material.
Test for chlorine. Chlorine is a greenish-yellow gas which
rapidly which reacts with chlorine:
bleaches damp litmus paper.
S 20aS - + 4C1, + 5H,0-* 2S0 4
2-
+ 8C1- + 10H+
Dry chlorine will not bleach. Pour about 20 cm of concentrated
3
Isotopes of chlorine

Chlorine has two principal isotopes. Both have the sulphuric acid into a gas-jar of the gas as soon as it is collected. After
electron ar-
rangement 2, 8, 7. One has an atomic nucleus of 17 protons and
a time put a piece of dry coloured cloth into the gas-jar. At the same
18
time put a piece of damp coloured cloth into a gas-jar of
chlorine;
neutrons (CI =35); the other has a nucleus of 17 protons and
20 remains un-
= the latter is immediately bleached, whereas the former
neutrons (CI 37). Ordinary chlorine (CI =
35.5) is a mixture of remains
these isotopes in the proportion of three of the lighter attacked. (If the chlorine and cloth are perfectly dry, the cloth
to one of the
heavier atoms. unbleached indefinitely.)

From the equation above, it is seen that water is necessary

Properties of chlorine
for the formation of hypochlorous acid, the compound
Chlorine a greenish-yellow gas with a choking, unpleasant,
is which liberates the oxygen and whicli performs the bleach-
irritating smell. Itis very poisonous if inhaled to even
a small extent ing. Hence, if no water is present no bleaching can occur.
(1 part of chlorine in 50 000 of air may be injurious).
It was used
extensively during the war of 1914-18 and, being about Chlorine as an element which combines readily with hydrogen to form
2± times as hydrogen chloride
dense as air, it would roll along the ground when propelled
by a very
gentle wind without a great deal of it escaping upwards. (Bleaching can also be considered under this heading)

It bleaches damp litmus and is a very reactive Exposure of chlorine water to sunlight. Pass chlorine gas into water
gas indeed. The fol-
lowing experiments illustrate its properties and they in a beaker for some time until the water
becomes quite yellowish
are classified it in
according to the various ways in which the gas can green in colour. Fill a long tube with this chlorine water, invert
act. sunlight
a beaker containing some of the water and expose to bright
Chlorine as a bleaching agent (Fig. 1 14). After some time, a gas collects in the tube
and on applying
a glowing splint, the latter is rekindled, showing the gas to be oxygen.
Pour a little litmus solution into a gas-jar of the gas. The
litmus
immediately turns colourless. Chlorine will bleach the colour
from
2C1- + 2H,0 -*• 4HC1 + 2

most dyes and will remove writing ink (but not printer's ink, combined with the hydrogen of the water to form
chlorine has
which The
consists mainly of carbon, which chlorine does not
attack). hydrogen chloride and oxygen is liberated.
Bleaching action. The chlorine reacts with the water, forming
hypo- The above reaction probably occurs in two stages, as indicated by
chlorous acid.
the equations:
Cl 8 + H 2 -> HOC1 + HC1 H,0-f Cl 2 -»- HOC1 + HC1 (instantaneous)
chlorine water hypochlorous hydrochloric water chlorine hypochlorous hydrochloric
acid acid acid acid
 360 A NEW CERTIFICATE CHEMISTRY PROPERTIES OF CHLORINE 361

2HOC1 -»- 2HC1 +O t (slow) Turpentine (a hydrocarbon) consists of hydrogen and carbon in
oxygen
chemical union. The chlorine combines with the
hydrogen and leaves
The burning of hydrogen in chlorine. Lower a jet of burning hydro-
the black carbon behind.
gen (great care before lighting, see p. 269) into a gas-jar full of
C 10
8Cl (g) -+ 10C(c)
H l9 0) + g
16HCl(g) +
chlorine. The hydrogen continues to burn with a white flame and
burning taper. into a
Lower a burning taper
clouds of steamy fumes of hydrogen chloride are seen, whilst the Effect of chlorine on a
gas-jar of chlorine. It burns with a small, red and sooty flame. Wax
yellowish-green colour of the chlorine gradually disappears.
with the turpentine, the

hydrogen
H, + CI,
chlorine
- 2HCI hydrogen
consists mainly of hydrocarbons and, as
hydrogen forms hydrogen chloride and leaves the carbon.
of hydro-
chloride Action of chlorine on hydrogen sulphide. Invert a gas-jar
sulphide over a gas-jar of chlorine and remove the plates. You
gen
Oxygen
will observe a yellow precipitate of sulphur,
and hydrogen chloride
r .

will be formed.
H3 S + CU -+ 2HCI + S
hydrogen chlorine hydrogen sulphur
sulphide chloride
oxidation-reduction, in which
>t>
This can also be regarded as a case of
sulphide ion
chlorine is reduced to its ions by electron gain and the
Chlorine is the
(from H a S) is oxidised to sulphur by electron loss.

hydrogen sulphide the reducing agent.

oxidising agent,
[ H 2 S ^ 2H+ + S»-
. C/i/orme. [S*-
{!
—> S + 2e~ (oxidation)
water
Cl s + 2e~ -* 2C1~ (reduction)

Chlorine as a chloride former

Chlorine is a very reactive element and will combine with
most
elements to form chlorides. In many cases chlorine will com-
other
applying a flame or in
bine with elements spontaneously, i.e., without
take place.
any way inducing the reaction to
Action of chlorine on phosphorus (a non-metal). Lower a
piece of

yellow phosphorus into a gas-jar of chlorine. It burns spon-

Fio. 114. dry
Exposure of chlorine water to sunlight. taneously, giving off white fumes of chlorides of phosphorus.
P4 + 6Cl 8
->-4PCl 3
The readiness with which hydrogen and chlorine combine together is phosphorus
so great that, if a tube containing equal volumes of chlorine and trichloride

hydrogen is exposed to sunlight, it explodes. P4 -f 10Cl s -»-4PCl 5

Action of chlorine and warm turpentine. Warm a little turpentine in phosphorus
pentachloride
a dish, dip into it a filter-paper, and then drop this into a gas-jar of
chlorine. There is a red flash accompanied by a violent action whilst In the following cases the reactants are all metals.
a black cloud of solid particles of carbon is also formed. Hydrogen Action of chlorine on sodium. Lower a piece of burning sodium on
burn,
chloride can be shown to be present by blowing the fumes from an a deflagrating spoon into a gas-jar of chlorine. It continues to
ammonia bottle across the top of the jar, when dense white fumes of giving off white clouds of sodium chloride.
ammonium chloride are observed. 2Na + CI 2
->-2NaCl
sodium chlorine sodium
NH 3 (g) + HCl(g)-> NH 4
+
CI-(c) chloride
 362 A NEW CERTIFICATE CHEMISTRY PROPERTIES OF CHLORINB 363

Action of chlorine on copper. Drop a piece of Dutch metal (a very The electrons for this purpose are supplied by the reducing agents
with which the chlorine is reacting. In the two cases
thin sheetof an alloy of copper and zinc, mainly copper) into a gas- given below,
jar of chlorine. It burns spontaneously with a green flame these are
to form
copper(!I) chloride and a little zinc chloride. (a) The ironfll) ion, which is oxidised to the ironfJIT) ion by

Cu + CI,-»-CuCl, electron loss,

Fe*+ - e~ -* Ft?+
copperdl)
chloride oxidised
(b) The sulphite ion, which, in association with water, is

Zn + CI, -»- ZnCl, to the sulphate ion,

zinc
chloride S0 32 " + H,0 - 2e~ -> SO a - + 2H +
t

Action of chlorine on iron. Place a coil of iron wire in the hard-glass also with electron loss.
tube in the apparatus shown in Fig. 115 and pass a stream of pure dry (a) Action on iron(IT) chloride
solution. Bubble a stream of chlorine
chlorine over it. On heating the wire by means of a burner, the wire of iron(II) chloride (which is pale green in colour).
through a solution
glows and the reaction continues without application of the flame, changes to yellow, and on adding a little caustic alkali
The colour
black crystals of ferric chloride, or iron(III) chloride, collecting in reddish-brown precipitate of iron(III)
the solution there is obtained a
small bottle, which acts as a condenser. the iron(II) chloride has been oxidised to
hydroxide, showing that
2Fe + 3Cl,-»-2FeCl 3
iron(III) chloride.
2FeCl 2 -r-Cl,-»-2FeCl 3
iron chlorine iron(III)
chloride or 2Fe* + + Cl I ^-2Fe^-f-2Cl-
Note that the iron (III) salt formed— an sulphuric acid. On bubbling
indication that chlorine of sulphurous acid to
is
(b) Oxidation
is an oxidising agent. acid in water for a few minutes,
chlorine into a solution of sulphurous
The black crystals of anhydrous iron(HI) chloride should be dilute sulphuric acid is obtained.
removed
and placed ina desiccator, as they are very deliquescent. 2H,0 + SO, + CI, -^ H aS0 4 + 2HC1 -
H,0 + SO, ^ H,S0 3 ^ 2H+ + SO,
1
or
Fume SOs*- + H sO + Cl,-> S0 4 + 2H+ +
to »- 2C1-
chamber testing with
The presence of the sulphuric acid can be shown by
calcium chloride hydrochloric acid and barium chloride before and after the
dilute
is obtained after the experiment a
white precipitate
experiment. There
sulphate. [N.B. The sulphurous acid solution must be fresh,
iron wire of barium
of sulphuric acid due to
chlorine otherwise it will contain a certain amount
mmsmmma atmospheric oxidation.]
Anhydrous
calcium — To prevent
Y The displacing action of chlorine

Chlorine can displace bromine and iodine

from bromides and
chloride
condensation of iodides. . . ,
. . ,
solution of potas-
iron(m) chloride here Displacement of bromine. Bubble chlorine into a
immediately turns red
Fio. 115. sium bromide in water. The clear solution
a drop of a red
(due to formation of bromine water) and
finally
Preparation of iron(III) chloride.
bottom of the boiling-tube.
liquid (bromine) is observed at the
Chlorine as an oxidising agent
2KBr + Cl,-v2KCl-f Br,
In its oxidising behaviour, chlorine, like other oxidising agents, The above experiment is repeated with
Displacement of iodine.
acts as an acceptor of electrons. It is converted to chlorine ions, as: The clear solution turns to the character-
potassium iodide solution.
CI f + 2«--*-2Cl- istic dark brown 'iodine' colour
and finally a black solid (iodine) is
 364 A NEW CERTIFICATE CHEMISTRY PROPERTIES OF CHLORINE 365

deposited. On warming the solution the characteristic violet vapour Manufacture. Slaked lime is moved forward by Archimedean screws
of iodine is seen. through a series of pipes against a counter-current of chlorine until
2KI + Cl,-*-2KCl + I t
the requisite weight of chlorine has been absorbed. The solid is
In these two reactions, chlorine oxidises the ions, Br" and I - , by removed and packed.
It contains about 36% of available
chlorine, i.e., chlorine which
attracting the electrons from them, and chlorine is reduced to its ions
can be removed by dilute acids and even by the carbonic acid of the
by electron gain.
atmosphere. Hence bleaching powder usually smells of chlorine and
2Br- (or 21") + Cl -* Br 2 (or LJ + 2C1- deteriorates if in contact with air. It has an extensive use in dye works,
8

Act ion of chlorine on the caustic alkalis laundries and even in the home.
On the cold dilute aqueous solution.
Chlorine is absorbed by a solu- CaOCl 2 + CO, -* CaC0 3 + Cl 2
bleaching carbon chlorine
tion of water ofsodium hydroxide or potassium hydroxide, forming powder dioxide
a pale yellow solution of the hypochlorite and chloride of the metal.
2NaOH -* NaOCl + NaCl + H
Cl 2 -f
2
Chlorine in chemical industry
Cl 8+ 2K.OH -> KOC1 + KC1 + H 2 (a) Chlorine is extensively used as a bleaching agent and in the
or d a + 20H- -> OCI- + CI" + H aO manufacture of bleaching agents and domestic antiseptic solutions
On the hot concentrated aqueous solution. If chlorine
is passed into such as sodium hypochlorite. It is also used in the manufacture of
a hot concentrated solution of potassium hydroxide for some time, chlorates, used, for example, as weed-killers, and in the manufacture
there is formed a mixture of potassium chloride and potassium chlor- of hydrogen chloride. This gas is used in the production of PVC
ate, and the latter can be obtained by crystallising the mixture when (p. 461) so that chlorine is indirectly involved in this product.
crystals of potassium chlorate separate first. (These can be purified (b) Many organic chemicals are manufactured with the
help of
by recrystallisation.) chlorine, e.g., carbon tetrachloride, CC1«, trichloroethylene, C 2 HCI 9 ,

CCl 3 .CHO and many others. These compounds are useful

6KOH + 3C1 2 -> KC10 3 + 5KCI + 3H a O chloral,
potassium potassium as degreasing agents, dry-cleaning fluids and as sources for other
potassium
hydroxide chlorate chloride products, e.g., chloral for DDT.
or 60H- + 3C1 -> C10 3 - + 5C1 - + 3H.O
8 (c) Chlorine is used in sterilising water for domestic and industrial
A similar action is observed if hot concentrated
sodium hydroxide use and for swimming-baths.
solution or milk of lime is substituted for the potassium Chlorine occurs as an important by-product of electrolytic cells
hydroxide
solution. which produce sodium hydroxide from the raw material, sodium
chloride. For this, see p. 253. The products appear in the
mass pro-
Notice that in the above actions the alkalis are dissolved (or sus-
pended) in water. portion of NaOH CI, i.e., 40 35.5.
: :

In the older Deacon's Process, hydrogen chloride (produced

from
Bleaching powder sodium chloride and concentrated sulphuric acid) was oxidised by air
copper(II)
If chlorine is passed for a considerable time over solid to chlorine at about 450°C in the presence of the catalyst,
slaked lime available
the product is bleaching powder, formerly chloride, CuCl„ distributed on broken brick to increase the
used as an easily trans-
ported substitute for free chlorine. Now, however, surface.
liquid chlorine is
regularly transported in bulk and bleaching
powder is less important. 4HC1 +O t
-*• 2H a O + 2C1,
Laboratory preparation. Take a gas-jar full of chlorine
and shake a
teaspoonful of freshly prepared slaked lime into it. This process (introduced in 1868) was apparently rendered obsolete
The colour of the
chlorine disappears immediately. The product by electrolytic processes about 50 years later but has been recently
may be used to absorb
the chlorine from revived.
several more gas-jars before absorption is complete.
(For an account of chlorine as a member of Group VII of the
Ca(OH) 2 + CI, -»- CaOCl„.H 2 Periodic Table, see p. 85. For chlorine molecule, see p. 375.)
calcium chlorine bleaching
hydroxide powder {Questions on page 385)
 HYDROCHLORIC ACID 367

The reaction proceeds in the cold, although a further yield of the

gas was obtained in the industrial process by heating to a red heat.
NaCl + NaHS0 -> Na S0 +
4 a 4 HC1
sodium sodium sodium hydrogen
Chapter 27 chloride hydrogen
sulphate
sulphate chloride

(The above indicates clearly the acid nature of sodium hydrogen

sulphate.)
A solution of the gas in water can be made by
Hydrogen Chloride and the Chlorides
means of the funnel arrangement as in Fig. 117.
This solution is hydrochloric acid. If the gas is
passed into water until no more gas is absorbed,
HYDROGEN CHLORIDE the product is concentrated hydrochloric acid

THE gas usuallyis hydrogencalled chloride, or hydrochloric acid and contains about 36% by weight of hydrogen
whereas the solution
gas, of the gas in water (which when satur- chloride.
ated contains about 36% by weight of the gas) is termed hydrochloric This device of passing a gas into water by
acid. means of an inverted funnel is essential when Fio. 117.
the gas very soluble in water. If the gas is suffi-
is Method of dissol-
Preparation
ciently soluble, it may be absorbed in the water ving a very soluble
gas in water.
Common (sodium chloride) is placed in a flask fitted with a
salt more quickly than it is being generated in the
thistle funnel and delivery-tube, and concentrated sulphuric acid is flask. In this case, the pressure in the delivery-
added (Fig. 116). There is effervescence, and misty fumes are ob- tube and flask is reduced and atmospheric pressure from outside
then forces the water back up the delivery-tube. This effect is called
'sucking-back'. If the tube is made of ordinary narrow glass
tubing, the water will quickly fill it and pass over into the generating
if hot
flask. This would in any case stop the reaction and might,
concentrated sulphuric acid was being used, be dangerous. When the
inverted funnel is used, the water may begin to suck back, but
Common Salt ' a
and cone. funnel before the
Sulphuric considerable volume of it is required to fill the
acid narrow tube is reached. This lowers the level of the water in the
beaker, and, if the rim of the funnel was at first only just
immersed,
and air will be forced under it, before the funnel
it will be exposed,
is filled. soon as air enters, the water drops back from the funnel
As
that, to be effective,
\ Concentrated to the beaker and the process begins again. Notice
Sulphuric acid the funnel must be arranged with its rim only just immersed.
An
to dry the gas water surface
additional advantage is that the funnel offers a large
Fio. 116.
for absorption of the gas.
Preparation of hydrogen chloride.

Test for the gas

served. The gaspassed through a wash-bottle containing concen-
is
appears misty), acid
trated sulphuric acid to dry it, and collected It isa clear gas (although in damp air it
as shown by downward
white precipitate of silver chloride m a
delivery, the gas being denser than air. to litmus, and produces a
of silver nitrate and nitric acid which is held on a
drop of a solution
H*S0 4(l) + NaCI(c) -*• NaHS0 4 (c) + HCl(g)
glass rod in the gas.
or H s S0 4 + CI- ->• HS0 4 - + HC1
366
Ag+(aq) + Cl"(aq) -»- AgCl(c)
 368 A NEW CERTIFICATE CHEMISTRY CHLORIDES 369
Properties termed a 'constant
chloric acid, which distils over unchanged. This is

It has a choking, irritating smell, and is an acid gas, which is very boiling mixture'.
soluble in water. These latter two properties are neatly shown by the
fountain experiment (Fig. 138). In this case, blue litmus is placed in the Manufacture of hydrogen chloride
trough and turns red in the flask, showing the acidity of hydrogen Until recently, hydrogen chloride was manufactured exclusively by
chloride in aqueous solution. heating common salt with concentrated sulphuric acid. This was the
first stage of the Leblanc process.
Hydrochloric acid 2NaCl + H,SO t -»• 2HC1 + Na S0 4 2

This is a solution of hydrogen chloride in water. Being almost in water to form hydrochloric acid.
The gas was absorbed
completely ionised in dilute solution, this acid is very strong, and
Recently, improved methods of manufacture of hydrogen have
shows the usual acidic properties (p. 223), as made it possible to produce hydrogen chloride in quantity by direct
HC1 -* H+ + CI- combination of hydrogen with chlorine, which is obtained by electro-
(i) liberation of hydrogen with certain metals (Mg, Zn, Fe): lysis of brine.
H2 + Cl 2 -* 2HC1
Zn + 2H+ -* Zn* + + Hg
neutralisation This method is likely to increase in importance.
(ii) of bases to form salts and water
Na + OH- + H + CI- -> Na+ Cl~ +HO s
(iii) liberation of carbon dioxide from carbonates CHLORIDES
2H- + C0 3a -->H s O + C0 2
Metallic chlorides
In (i), notice, however, that hydrochloric acid does not react
with Preparation. All metals are attacked by chlorine to form chlorides.
copper. The methods of preparation are summarised below.
It may be mentioned here that the situation is The chlorides of these metals are made by the action of:
not quite as simple
as the above implies. Pure water-free HCI shows no acidity
because These metals are
it contains no ions. It is a covalent compound. the alkali (or oxide) or fK
The aqueous solution
carbonate on dilutes Ca attacked by dilute
1
contains ions. The ion responsible for acidity, however, is
not I he
simple H
+ ion, but a hydrochloric acid. iNa hydrochloric acid.
hydrated form of it, H 8 0+, produced by a
reaction between HCI and water: (Ma 1

the metal, oxide, or

Al l
H8
+ HCl-»-HaO + + a- carbonate on dilute<
Zn 1
Similarly, water-free H sSO« and HNO are probably hydrochloric acid.
Fe 1 All attacked by
not acidic (being
s
unionised), but ionise in water and then become strongly acidic:
chlorine to form
by double decom-,
H s S0 + 2H
4 2
->- 2H a O * + S0 4*~ position.
Pb a chloride.
HNO + H O ->- H O+ + N0
s a a 3
- These metals not
the oxide or carbon- attacked by dilute
For ordinary purposes the hydration of the hydrogen ion is often Cu
ate on dilute hy-] hydrochloric acid.
ignored and H+ is used. (For HCI in toluene,
see p. 240.)
Action of oxidising agents. Chlorine is the drochloric acid.
product of oxidation of
hydrochloric acid and most oxidising agents will by double decom-
liberate chlorine Ag
from it (see p. 355). position. i
Action of heat. If a concentrated made by the action of chlorine on the
hydrochloric acid solution is N.B. IronfJII)1 chloride is
heated, hydrogen chloride escapes into the
air. If a very dilute solu- metaL
tion is heated, water is lost, making the acid
more concentrated. In
both cases a mixture is finally obtained containing The chlorides of these metals are very deliquescent. The above is a list of
20.24% of hydro- »

common metals in the order of the electrochemical scries.

370 A NEW CERTIFICATE CHBMISTRY SODIUM CHLORIDB 371

Aluminium chloride, A1CI 3 is not deliquescent (the dampness of ordinary salt is due to impurities,
magnesium chloride which is deliquescent).
This is a pale yellowBeing readily hydrolysed by water, it
solid. e.g.,
fumes in damp of hydrogen chloride. If required
air with evolution Sodium chloride is a very important chemical. As a sodium com-
pound, it is converted into caustic soda, washing soda,
baking soda
anhydrous, it must be prepared by healing aluminium foil in dry
chlorine or dry hydrogen chloride. The apparatus is the same as for and salt-cake (sodium sulphate) and other less important sodium
iron(III) chloride (p. 362). compounds. It is used to 'salt-out' soap. As a chloride, it yields
hydrochloric acid and chlorine, used as a bleaching agent and in
2AJ +
3C1, -> 2A1C1 3
manufacture of hypochlorite solutions for home use, as well as in
2AI + 6HC1 -v 2A1C1 3 + 3H„
fine chemical manufacture.
The anhydrous solid reacts rather violently with water. It forms the
The alkali industry of south Lancashire and Cheshire is close to

the Lancashire coalfield and to common salt deposits at Northwich

hydrate, A1C13.6HS.O, and, with excess water, dissolves and hydro-
lyses considerably.
and to limestone outcrops. The neighbouring Lancashire textile area
AICI3 + 3H,0 ?* Al(OH) 3 + 3HC1 takes its products to manufacture soap and for bleach and dye in-
On evaporation to dryness, the solution leaves hydroxide as residue. manufacture in the area. The Mersey and
dustries; there is also glass
itscanal systems, and the Manchester ship canal, provide good bulk-
Ammonium chloride (sal-ammoniac), Nil .CI transport facilities.

This compound has many uses, two of the chief being as a consti- Sodium chloride crystallises as a
o -ci~
tuent of the Leclanche" electric battery, and as a flux in soldering. It face-centred cube (see diagram). In
is usually prepared by boiling ammonium sulphate solution with an end face of the cube as shown, a
common salt. Na + ion occupies the centre; then
the four corners of the face are also
(NH 4) 2 S0 4 + 2NaCl «* 2NH 4 C1 + Na 3 SO, occupied by Na + ions, with four Cl
-

On cooling,sodium sulphate crystallises first and may be removed by ions spaced equally between them. Sodium Chloride
Crystal lattice of
filtration, afterwhich ammonium chloride may be obtained from the In the next face, the positions of
filtrate as a white solid. It sublimes on being heated. For the action Na + and Cl~ ions are reversed, and
of heat on ammonium chloride see p. 433. so on alternately. The attractive forces between the ions are rela-
tively great. The only ionic motion is some vibration, consequently
Potassium chloride, KC1
the solid appears rigid and has negligible electrical conductivity.
This occurs as carnallite (K.Cl.MgCl 2 .6H 30). Potassium chloride When heated the ions vibrate increasingly; at 801°C the lattice col-
can be prepared in the laboratory by the neutralisation of potassium lapses, i.e., the salt melts and the ions become mobile. The fused salt
hydroxide solution with dilute hydrochloric acid. conducts electricity by migration of Na + to cathode and Cl~ to

KOH + anode where each discharged to give sodium and chlorine.

HC1 -» KC1 + H 8
is

Eotassium dilute potassium water 2Na + + 2e~ -* 2Na; 2C1" -» Cl 2 + 2e~

ydroxide hydrochloric chloride
acid The lattice arrangement in the solid is determined by X-ray diffraction.
Itforms white cubic crystals similar to those of sodium chloride. It A narrow beam of X-rays is passed through a crystal of the com-
imparts a lilac colour to the non-luminous Bunsen flame. It is not pound and on to a photographic plate. After development, the plate
deliquescent. shows a central spot, produced by X-rays which have passed straight
through the crystal, and, round it, a diffraction pattern of spots from
Sodium chloride, NaCl which the lattice arrangement can be deduced.
This occurs as a rock
salt, which is mined as solid or pumped out
of the ground as brine. It is prepared by similar methods to those Calcium chloride, CaCL
used for potassium chloride and forms white cubic crystals. It im-
This very deliquescent and can be used as a drying agent for
is
parts a golden yellow colour to the Bunsen flame. Pure common salt
most gases (but not for ammonia, with which it forms a compound).
372 A NEW CERTIFICATE CHEMISTRY SILVER CHLORIDE 373

The anhydrous salt is prepared by evaporating a solution until the FeCl, + 2NaOH 2NaCl + Fe(OH),
iron(II) iron(II)
solidformed fuses. The solution is most easily prepared by adding
chloride hydroxide
marble or limestone to dilute hydrochloric acid until a little of the
marble remains. The mixture is then filtered. ionically: Fe2+ (aq) + 20H"(aq) -> Fe(OH) 2(c)
CaCO a + 2HC1 - CaCl, + H O + CO,
g
Lead(ll) chloride, PbCl 8
Anhydrous ferric chloride, iron(lll) chloride, FeCl 3 This is a white insoluble substance made by the interaction of a
This is made by the action of iron on chlorine by the method solution of any soluble lead(II) salt with a solution of any soluble
described on p. 362. chloride.
The anhydrous salt cannot be made by the evaporation of the Into a beaker put some dilute hydrochloric acid and add lead(U)
solution because the chloride is attacked by water when a concen- nitrate solution. There is a white precipitate.
trated solution evaporated. This type of action is termed hydrolysis.
is
PrXNOs)* + 2HC1 -»- PbCl a + 2HNO,
/C\ HOH /OH ionically: Pb 2+
(aq) + 2Cl-(aq) -*• PbCl 2 (c)
Fef-jCl + HOH 'ef-OH + 3HClf Filter off the white precipitate, wash it two or three times with a little
\jCl HOH \OH cold distilled water and put it on a porous plate to dry.
Lead(II) chloride is almost insoluble in cold water yet fairly soluble
loses wa ter on heating in hot water. (It is the only common substance which shows this
peculiar behaviour.)
Fe,0 8

On heating the solution in air the final product is iron(III) oxide. Silver chloride, AgCl
This action is the reverse of neutralisation. This a white insoluble compound made by adding a solution of
is

Iron(III) chloride isa black solid in the anhydrous state, but forms any soluble silver salt to a solution of any soluble chloride.
a brown solution if concentrated, and a yellow solution if dilute. It
+ NaN0
and
AgNOg + NaCl - AgCll 3
can be reduced by reducing agents [e.g., zinc dilute hydrochloric silver sodium silver sodium
acid) to iron(II) chloride. nitrate chloride chloride nitrate

Zn(c) + 2Fea+ (aq) -> Zn 2+ (aq) + 2Fe8+ (aq) ionically: Ag" (aq)
1
+ Cl-(aq) -> AgCl(c)
With alkaline solutions, it gives (as do all iron(ITI) salts dissolved in The white solid is filtered off, washed two or three times with hot
water) a reddish-brown gelatinous precipitate of iron(III) hydroxide. water and dried on a porous plate. (The whole action should
distilled

FeCl a + 3NaOH -* Fe(OH) + 3NaCl 3

be performed in the absence of light since silver chloride turns violet
-> Fe(OH) 8 (c) on exposure to light.)
ionically: Fe8+ (aq) + 30H-(aq)
All the silver halides, AgCl, AgBr and Agl, emit electrons when
exposed to light (a photoelectric effect) and are slowly reduced, turn-
Ferrous chloride, iron(IT) chloride, FoCl,
ing violet and, eventually, black. The chief reduction product is
Anhydrous iron(H) chloride, a white solid, is made by heating iron metallic silver.
wire strongly in a stream of dry hydrogen chloride. Ag+ + e~ —* Ag
Fe + 2HCl-»-FeCl, + H t The halides show decreasing photoelectric activity in the order:
hydrogen hydrogen
AgBr -* AgCl —* Agl. This is why silver bromide is used as the
iron iron(II)
chloride chloride
principal silver compound suspended in the gelatine of a photo-
It forms a pale green solution which gives, with alkaline solutions a
graphic plate. The other silver halides are less sensitive to the action
dirty green precipitate of iron(II) hydroxide (as will any iron(U) salt
of light.
dissolved in water).
374 A NEW CERTIFICATE CHEMISTRY CHLORIDES 375

Properties of chlorides Divide the precipitate into two parts. Add ammonium hydroxide to
(1) Action with concentrated sulphuric acid. On being treated with one and observe that the precipitate dissolves. Allow the other to be
concentrated sulphuric acid, a chloride evolves hydrogen chloride, exposed to the light for a few minutes. The precipitate will turn violet.
e.g., Silver chloride is insoluble in nitric acid but soluble in ammonium
NaCl(c) + H 2S0 4 (1)-* NaHSO«(c) + HCl(g) hydroxide.
and
The only two common insoluble chlorides arc lead chloride
(2) Chlorides are more volatile than most salts.
silver chloride.
The chlorides are on the whole a volatile class of compounds. This
makes them suitable for use in the 'flame-test' in which certain metals
can be detected by the colour their vapour imparts to the Bunsen
flame. To perform the flame-test, the substance under consideration The chlorine molecule
is moistened with concentrated hydrochloric acid and a nichrome It is known by experiment (p. 112) that 1 volume of chlorine
or platinum wire is dipped into the mixture and applied to the non- combines with hydrogen (also 1 volume) to produce 2 volumes of
luminous Bunsen flame. hydrogen chloride in constant conditions. Applying Avogadro's Law
Metal chloride Co/our to the chlorine and hydrogen chloride, 1 molecule of chlorine pro-
duces 2 molecules of hydrogen chloride. Since the least possible
Sodium Persistent golden yellow
amount of chlorine in a molecule of hydrogen chloride is one atom
(invisible through blue glass)
(atoms being indivisible for chemical purposes), the molecule of
Potassium Lilac flame
chlorine must supply at least two atoms to the hydrogen chloride.
(visible through blue glass) That is, the chlorine molecule is at least diatomic. It is also known
Lithium Carmine
that chlorine has never produced more than twice its own volume
Copper Green (blue zone)
of any gaseous chlorine compound in constant conditions. This
Calcium Red points to an actually diatomic molecule for chlorine, i.e., C\ t .

Hydrolysis of chlorides. Several chlorides are readily hydro-

(3) Further, the specific heat of gaseous chlorine at constant pressure
lysed by water, e.g., magnesium, zinc and iron chlorides. If solutions is greater than its specific heat at constant volume in the ratio of

of the chlorides are evaporated a basic salt or the oxide of the metal 1.36: 1. This is close to the recognised value of 1.40 for diatomic
remains. gases.

(4) Action
of concentrated sulphuric acid on mixture of chloride and Questions on this chapter will be found on page 385.
oxidising agent. Mix together a little common salt and manganese
dioxide (many other oxidising agents would be suitable). Put this
into a test-tube, add a few drops of concentrated sulphuric acid, and
warm. A green gas, chlorine, is evolved.
2NaCl + 2H 2 SO« + MnO a -» MnSO« + Na,SO«
sodium concentrated manganese manganese sodium
chloride sulphuric dioxide sulphate sulphate
acid manganeseflV)
oxide
+ 2H.O + a,
water chlorine

Test for a soluble chloride

Dissolve a suspected chloride in distilled water and add a little
nitric acid and then silver nitrate solution. If a chloride is present you
will see a white precipitate of silver chloride.

Ag + (aq) + Cl-(aq) -> AgCI(c)

 BROMINB 377

which condenses to a red liquid in the cooled receiver. This is

bromine.
2KBr +MnO, 2H a S0 4+ K,S0 4 -MnSO« + 2H sO + Br, +
bromine
potassium manganese concentrated
bromide (IV) oxide sulphuric
Chapter 28 acid

Cone Sulphuric add.

•Manganese Dioxide,
Bromine and Iodine and Potassium Bromide.

BROMINE
BROMINE was discovered by Balard in 1826. He passed chlorine
through the mother liquor obtained after crystallising common
salt from sea-water. The liquor turned red and from it he was able to
isolate bromine and to show that it was an element.
Liebig, some years previously, had received the dark red liquid with
a request to examine it, but thinking that it was merely a compound
of iodine and chlorine, he did not pay it much attention.

Occurrence
Fio. 118.
Bromine occurs chiefly as the bromides of potassium, sodium and
Preparation of bromine.
magnesium, usually in association with larger proportions of the
chlorides of those metals. Since the bromides are much more soluble
Physical properties of bromine
in water than the chlorides, a liquid rich in bromides is left by
Treated in this way, the mother liquors
crystallising out the chlorides. (1) It is a heavy (density = 3.2 g/cm 3
), red, volatile liquid (boiling-

from the Stassfurt deposits in Germany (which consist mainly of point 59°C).
(2) It has a choking, irritating smell. (Its name means 'a
stench'.)
carnallitc, KCl.MgCl2.6HjO), after the removal of a large proportion
of the potassium chloride contain about |% of bromide and the The liquid causes sores on the flesh, which heal with difficulty.
It is slightly soluble in water, forming a red solution
containing
bromine is obtained by allowing this solution to come into contact (3)
with chlorine, which displaces the bromine: about 3% of bromine at ordinary temperatures.
The following chemical properties are considered under the same
MgBr. + Cl,- MgCl 2 + Br, headings as those of chlorine.
magnesium bromine
bromide
Bromine as a bleaching agent
Laboratory preparation of bromine
Bromine is a bleaching agent, not so rapid as chlorine. A piece of
This experiment must be done in a fume-chamber.
damp litmus paper is bleached when placed in the vapour of bromine.
Bromine can be prepared in a way exactly analogous to one of the
methods for making chlorine.
Bromine with hydrogen
Make an intimate mixture of potassium bromide and manganese
dioxide (manganese(IV) oxide) and place this in a retort (Fig. 18).
Bromine combines with hydrogen, but not as readily as does chlor-
1

ine. A mixture of chlorine and hydrogen will explode when merely

Add some concentrated sulphuric acid and warm the mixture. A red
gas is given ofT(together with some misty fumes of hydrogen bromide) exposed to sunlight, but a mixture of bromine and hydrogen needs
376
378 A NEW CERTIFICATE CHEMISTRY HYDROGEN BROMIDE 379

the application of heat to induce combination, and the compound Summary

formed (hydrogen bromide) is not as stable as hydrogen chloride. Bromine is an element very similar to chlorine but differing from it

H, + Br,->-2HBr principally in that bromine is less active than chlorine.

Bromine as a bromide former HYDROGEN BROMIDE

Bromine combines readily with most metals and non-metals to not as stable as hydrogen
As indicated above, hydrogen bromide is
form bromides, for example, copper, iron, sodium, sulphur. It ex-
chloride and is decomposed to some extent by the action of heat.
plodes when mixed with yellow phosphorus, so vigorous is the action.
This, together with the fact that hot concentrated sulphuric acid is
Phosphorus tribromide is made by gradually adding a solution of
an oxidising agent, makes it impossible to prepare pure hydrogen
bromine in carbon tetrachloride to red phosphorus. The solution is
bromide by the action of heat on a mixture of concentrated sulphuric
used in order to moderate the action.
acid and potassium bromide. The products of such an attempt would
be hydrogen bromide, bromine and sulphur dioxide.
Bromine as an oxidising agent bromine on a mixture of red
It may be made by the action of
Bromine is an oxidising agent, Br, -f 2e~ —* 2Br _
, but not quite phosphorus and water. The chemistry of the action is that bromides
as vigorous as chlorine. It will perform the majority of the oxidations of phosphorus are formed which are decomposed by the water.
attributed to chlorine. Thus, on shaking an acidified solution of
iron(II) sulphate with a few drops of bromine in a test-tube, the Preparation of hydrogen bromide
bromine colour soon disappears and the iron(II) sulphate has been Make a paste of red phosphorus and water and place this in the
converted into iron(IH) sulphate. flask (sandmay be added to 'dilute' the mixture). Bromine is dropped
2Fes+ + Br, -»- 2Fe8+ + 2Br~ in gradually from a tap-funnel and the reaction proceeds at ordinary
temperature (Fig. 119). Heat is evolved during the process and a
The displacing action of bromine amount of bromine may be volatilised and would, if not
considerable
removed, contaminate the hydrogen bromide. The bromine is
Bromine can displace iodine from iodides but cannot displace
chlorine from chlorides. Thus,
removed by passing it through a U-tube containing beads smeared
on adding a few drops of bromine to a
solution of potassium iodide in water, the characteristic brown colour
Bromine
of the solution of iodine in potassium iodide is seen. On boiling the
solution the violet vapour of iodine may be observed.
2KI + Br 2 -»-2KBr + I,
or 2I- + Br,-»-2Br- + I 1 Stiff paste.
of /fid
Action of bromine on the alkalis Phosphorus,
Sard and
The action of bromine on an alkaline solution is exactly analogous Water
to that of chlorine. Thus:
bromic
Cold potassium hydroxide solution
acid
2KOH + Br,-*KBr + KBrO + H,0
potassium potassium
bromide hypo-
bromitc
Hot potassium hydroxide solution

6KOH + 3Br, -»- 5KBr + KBrO, + 3H O t

Fio. 119.
potassium
bromate Preparation of hydrogen bromide.
380 A NEW CERTIFICATE CHEMISTRY IODINE 381
with red phosphorus and water. This U-tube is, in fact, a secondary
(iii) It is less stable than hydrogen chloride, being more easily
generating apparatus so arranged as to offer a large area of phos-
decomposed into its elements.
phorus to the bromine so that it is as completely removed as possible.
(iv) It is, in its general chemical properties, similar to hydrogen
The misty gas, very similar in appearance to hydrogen chloride, is chloride.
collected by displacement of air as shown in Fig. 119, the gas being
denser than air. It can also be dissolved in water to form hydro- Bromides
bromic acid by the apparatus shown on p. 379.
The bromides are prepared, generally speaking, by the same
4P + 6Br, —> 4PBr 8 methods as the chlorides and possess similar properties. They can
phosphorus bromine phosphorus readily be distinguished from the chlorides by the action of chlorine
tribromide
gas which has no effect on the chlorides but displaces bromine from
PBr s + 3H O -> H 3 PO a -f
a 3HBr bromides (see p. 378 for experimental details).
phosphorous hydrogen
acid bromide
(Alternatively hydrogen bromide may be prepared by heating
IODINE
potassium bromide with cone, sulphuric acid diluted with half its own
volume of water.) Iodine was discovered in 1812 by Courtois. He treated with con-
centrated sulphuric acid the mother liquors obtained after extracting
Preparation of hydrogen bromide from its elements sodium carbonate from the ash obtained by burning seaweed (kelp).
The gas can also be made by bubbling hydrogen through a wash- The ash contains a small percentage of iodides and the concentrated
bottle containingbromine and passing the gases through a heated sulphuric acid formed hydrogen iodide and oxidised it to iodine.
tube containing platinised asbestos, which acts as a catalyst. Any Gay-Lussac and Davy investigated the properties of the black solid,
unattacked bromine is absorbed by red phosphorus. which was called iodine by Gay-Lussac.
Most of the iodine used today occurs as calcium iodate, Ca(IO s)t,
H, + Br 2 -*-2HBr in the sodium nitrate deposits in Chile. The amount is very small
(about 0.1% but after the removal of the sodium nitrate by crystal-
Preparation of hydrogen bromide by the action of hydrogen sulphide
lisation the proportion is much higher in the residues. The iodine is
on bromine-water
obtained by treatment with sodium hydrogen sulphite.
A
convenient method for making a solution of hydrogen bromide
is bubble hydrogen sulphide through bromine-water for some time.
to Laboratory preparation from potassium iodide
Sulphur precipitates and can be filtered off. Grind together some potassium iodide and manganese dioxide
H,S + Br -)-2HBr-|-S| (manganese(IV) oxide) in a mortar and place the mixture in a dish.
2

Test. Hydrogen bromide turns damp blue litmus paper

red, and gives a pale yellow precipitate of silver bromide Black crystals
with a mixture of silver nitrate solution and nitric acid. oF Iodine
The precipitate is only slightly soluble in aqueous ammonia.
Cone. Sulphuric acid.
Ag'(aq) -(- Br-(aq) -* AgBr(c) Manganese Dioxide,
and Tolassium Iodide
Properties of hydrogen bromide

(i) It is a dense fuming gas with a choking smell (density = 2.8:

air = 1).
(ii) It is very soluble in water, forming a strongly acid
solution. A
saturated solution of hydrogen bromide contains about 70% by
weight of hydrogen bromide at ordinary temperatures. Fio. 120.
Preparation of iodine
382 A NEW CERTIFICATE CHEMISTRY HYDROGEN IODIDE 383

Add concentrated sulphuric acid and place an inverted funnel over and a little water, and pour this into the boiling water and stir. Allow
the dish as shown in Fig. 120. Warm the mixture carefully and the to cool, or if the starch paste is required immediately, pour some of
violet vapour of iodine will be seen to condense on the cooler parts of the paste into a boiling-tube and cool under the tap.
the funnel to black shining plates. The chemistry of the action is Add the smallest possible quantity of a solution of iodine (the test
similar to the formation of chlorine from common salt. The hydrogen is one part in one million) and immediately you will
sensitive to
iodide is, however, much more easily oxidised than even hydrogen observe a blue coloration. Warm the mixture and the blue colour
bromide. (For iodine molecule and crystals, see p. 75.) will disappear, but will return on cooling.
Mn0 + 2 2K1 + 2H 2 S0 4 -»- K 2 SO« + MnS0 4 + 2H tO + I, This test is given only by free iodine and is not given by, say, a
potassium iodine solution of potassium iodide in water.
iodide

Uses of iodine
Properties of iodine
The antiseptic properties of iodine have caused a large increase in
a black shining solid. Density 4.9 g/cm -3
(i) It is .
the demand for iodine during the last few years. It is sold as 'tincture
(ii) It sublimes when heated rapidly, forming a violet vapour

which the black solid can again be obtained by cooling.

from of iodine' — a solution of iodine
in dilute alcohol. It is used as iodine
and iodides medicine to treat cases of goitre, which disease is
in
(iii) It is almost insoluble in water but readily soluble
in potassium
thought to be due to lack of iodine in the body. Small amounts of
iodide solution. This is due to the formation of a compound of
iodine have, in fact, been shown to be essential to the human body
potassium iodide and iodine, KI 3 which readily dissolves. This
,
and all other forms of vertebrate life. Remarkable results have been
solution is brown. It also dissolves in alcohol and ether, forming
obtained by giving poultry a small but regular dose of potassium
brown solutions, and in carbon disulphide and chloroform, forming
iodide. The production of eggs was wonderfully increased.
violet solutions.
The following chemical properties of iodine are considered in the
same order as those of chlorine and bromine. HYDROGEN IODIDE
Iodine does not bleach, and has little affinity for hydrogen. The
This gas is much less hydrogen bromide. A
stable than even
effect of heating hydrogen iodide is to decompose the compound into
solution of hydrogen iodidewater quickly darkens because of the
in
its elements.
formation of iodine. It is usually prepared by the action of water on a
Iodine as an iodide former. Iodine is a fairly active element and will
mixture of red phosphorus and iodine. Since iodine is a solid and
combine with many metals to form iodides, but it does so much less
does not volatilise to an appreciable extent during the reaction, there
readily than either chlorine or bromine.
is no need for a U-tube as in the case of the similar preparation of
Oxidising action of iodine. Iodine is a mild oxidising agent. It will
not perform many of the ordinary oxidising actions attributed to hydrogen bromide (Fig. 119).
chlorine and bromine. It will, however, oxidise hydrogen sulphide to
If the tube, is heated hero
form hydrogen iodide and liberate sulphur. violet vapours of
Iodine are observed
H 2 S + I2 -*2HI + S|,
Action of iodine on alkaline solutions. The action of iodine with
alkalis is similar to the reactions of chlorine and bromine with
alkalis. Hypoiodites, iodides and iodates are produced (p. 364).
Displacing action of iodine. Iodine cannot displace chlorine or lodin*. red Solution of With Ammonh
bromine from chlorides or bromides. Phosphorus Silver rubrate .forms Wi
and 'a little gives yellow fumes of
water preapitate.\^ Ammonium
Action of iodine with starch solution iodide

Place a 400 cm 3
beaker full of water on a tripod and gauze and heat
Fig. 121.
to boiling. Make a paste of a small amount of starch (about 1
g) Simple apparatus to show some of the properties of hydrogen iodide.
384 A NEW CERTIFICATE CHEMISTRY QUESTIONS 385

For class purposes, the reactions of hydrogen iodide can easily be Comparison of halogen elements, Cl„ Br, and I, (see also p. 85)

shown by the very simple apparatus shown in Fig. 121. Grind a little These elements show very marked similarity of properties because all
red phosphorus with iodine in a mortar and introduce the mixture have seven electrons in the outermost electron shell.
into a dry boiling-tube. Add about four drops of water, insert a cork CI 2,8,7 Br 2,8,18,7 12,8,18,18,7
fitted with delivery-tube, and allow the gas to fall (hydrogen iodide is They are all univalent, forming an ion by gain of one electron per atom.
four times as dense as air) into test-tubes, one containing silver This completes the external octet.
nitrate solution and the other containing a few drops of ammonia. —
X, + 2e~ > 2X", where X is CI, Br or I
The tube may also be heated when the decomposition of the gas is Being electron acceptors, they are all non-metals and oxidising agents;
obvious from the violet vapour of iodine which is observed. chlorine is the most powerful oxidising agent and iodine the least. Typical
oxidations are:
4P + 6I 2 -»-4Pl3 2Fe'+ + CI, —* 2Fe*+ + 2C1" (iron(II) ion to iron(III) ion)
PI 3 + 3H s O-»- 3HI + H 3 P0 3 S»- + Br, —> S + 2Br- (H,S to sulphur)
phosphorus hydrogen phosphorous
tri-iodide iodide acid Because of their very marked oxidising action, chlorine and bromine are
bleaching agents; iodine is not.
A solution of hydriodic acid can be more simply obtained by In the order: CI — —
* Br * I, each halogen displaces an element to the
bubbling hydrogen sulphide into a suspension of iodine in water. right of it from simple salts. To do this, the more powerful oxidising agent
The end of the reaction is reached when all the iodine is seen to have oxidises the ion of the other halogen, so liberating the element.
disappeared. The precipitated sulphur is filtered off. CI, + 2Br- -* 2C1- + Br,
H,S +I -*2HI-r-S| Br, + 2I-->2Br- + I,
a
All three halogens behave in a similar way with aqueous caustic alkali
Test. Add a chlorine-water to a gas-jar of the gas,
little solution.
and pour a few drops of the liquid into starch paste. A Cold dilute: X, + 20H" —* X" + XO~ + H.O
blue colour is observed. Hot cone: 3X, + 6OH-—»• 5X" + XO," + 3H aO,
Properties. Hydrogen iodide
a fuming, choking gas, very soluble
is
where X is CI, Br or I. For names of products, see p. 364.

in water, forming hydriodic acid. The gas readily dissociates (rever- The silver salts of the three halogens, AgCl, AgBr, Agl, are all insoluble
in water and in dilute nitric acid. In the order given, they show gradation of
sibly) above !80°C.
—
colour: white pale yellow —*
yellow, and gradation of solubility in
2HI ?*H, +l s
ammonia : very soluble —
slightly soluble —
* insoluble. All the silver salts
are blackened by exposure to light, with reduction to metallic silver.
The acid, usually used as acidified potassium iodide solution, is a
All these halogens combine directly with hydrogen (chlorine most readily,
vigorous reducing agent (21" — —
2e~ > T 2 ). It is oxidised with liber- iodine least) and the halides, HC1, HBr, HI, are gaseous in ordinary con-
ation of iodine (brown) by exposure to air and by ditions, very soluble in water and strongly acidic. The gases show a grada-
hydrogen peroxide tion of stability, being stable up to 1500°C, 800°C and 180°C respectively.
Chlorine exhibits a covalency of seven, i.e., the number of electrons in
H a 2 -f 21- + 2H+ -> 2H 2 +I 2 the outer shell, forming the acidic oxide, C1,0,. Neither of the other halo-
potassium permanganate gens shows this maximum valency towards oxygen; iodine forms the acidic
oxide I,0„ but bromine forms no stable oxide.
2MnO«- + 101- + 16H' ->• 2Mn 2+ + 8H aO + 51,

Iodides

Iodides are similar to chlorides and bromides but can be readily

QUESTIONS ON THE HALOGENS
distinguished by the action of chlorine or bromine, which liberate 1. 'Chlorine the product of the oxidation of hydrogen chloride.*
is
iodine. Illustrate this statementby describing two different processes for the pre-
2KI + Cl 2 ->-2KCl + I!
paration of chlorine, one used in the laboratory and the other a large-scale
process. State the various stages in the bleaching of coloured cloth by
Addition of silver nitrate in dilute nitric acid to an iodide solution means of bleaching powder. (N.U.J.B.)
precipitates silver iodide, a yellow salt which is insoluble in ammonia. 2. Describe a laboratory method for preparing chlorine. What im-

Nal + AgNQ -*- Agl NaNO, purities would the gas so prepared be liable to contain, and how would
3 -f
you get rid of them? (O. and C.)
 NEW QUESTIONS 387
386 A CERTIFICATE CHEMISTRY
3. How would you prepare chlorine from bleaching powder ? What takes Under what conditions does this element combine with
liquid bromine.
does the compound so formed resemble and
differ
place when (a) a mixture of chlorine and hydrogen is exposed to diffused hydrogen? and how
daylight? (6) chlorine is passed into cold, dilute potassium hydroxide compounds of chlorine and iodine I (L.)
from the corresponding
solution ? (c) chlorine is passed into hot, concentrated potassium hydroxide
15 How would you make an
aqueous solution of hydrochloric acid
solution? (d) chlorine water bleaches litmus solution? (D.) chloride? Sketch the apparatus you would use What
starting from sodium
4. How can it be shown that hydrogen chloride contains half its volume show that the solution you have made is (a) aaa%
tests would you apply to
? Give one test in each case Hot
of hydrogen? acid
-would you determine
(5 hydrochloric
Contrast the behaviour of hydrogen chloride with hydrogen iodide (a) volume composition of hydrogen chloride ? (C.W.B.)
the
when heated; (6) when mixed with bromine vapour (O. and C.) dry chlorine. Explain
1 Describe the preparation and the collection of
contrast it with that of sulphur diox.de
5. Describe how you would prepare a specimen of bleaching powder in the bleaching action of chlorine and
cloth by
the laboratory. What happens when it is treated with (a) dilute hydrochloric How would you remove an ordinary ink stain from a white cotton
acid; (b) an acidified solution of iron(ll) sulphate? Describe how you means of bleaching powder? (L.)
would employ your specimen of bleaching powder to bleach a piece of red displacement of bromine, by
17 Explain in electronic terms the
cloth. (O.) aqueous potassium bromide solution. Why can this
chlorine, from i

a redox (oxidation-reduction) reaction? Why, in

6. Describe the preparation from iron of (a) chloride;
ironfl!) reaction be regarded as
chlorine from chlondes?
(b) iron(III) chloride. How may these compounds be converted one into Sonic ternTs, does iodine not displace,
periodic table and in a later period
the other? (O. and C.) Astatine, At, being in Group VII of the
iodine, what reaction would you expect between iodine and a
7. Give an account of the experiments you would do in order to in- Than
vestigate the action between lead dioxide and hydrochloric acid. By what metallic astatide? Justify your expectation.
electrons in the atoms of chlorine,
tests would you identify the more important products? (L.) 18. Quote the arrangement of
bromine and iodine. Explain in electronic terms the formation of (a) the
8. Chlorine will react with the substances slaked lime, iron, potassium
! (Sthe molecule, I„ (c) the molecule POC1, W) the molecule
hydroxide, hydrogen sulphide, potassium iodide and water. ion Cl ,
the oxidising power of these three
halogen atoms
Describe briefly the apparatus you would use in carrying out these re- CC ,. Briefly compare
State wi h reasons what you
actions and state clearly the conditions necessary to bring about the as shown in their behaviour with hydrogen.
the element astatine,
chemical change. Where possible, give an equation for the reaction. (D.) would expect as the behaviour of hydrogen with
which has^tomic number of 85 and is in Group VII of the periodic table.
9. Describe and explain the action of chlorine on (a) metallic sodium;
(b) sodium hydroxide solution; (c) potassium iodide solution.
An excess of chlorine water was added to 50 cm 3 of a solution of sulphur
dioxide. An excess of barium chloride (BaCI.) solution was then added
and the resulting precipitate after filtering, washing and drying, weighed
0.5202 Calculate the volume of sulphur dioxide at s.t.p. which was
g.
dissolved to make the original solution. (Ba = 137; S = 32.) (L.)
10. Suggest simple experiments by which you could show that (a)
ammonia contains hydrogen; (_b) carbon dioxide contains carbon; and (c)
common salt contains chlorine. (N.U.J.B.)
11. (a) Describe with a sketch how you would prepare and collect some
dry chlorine.
(b) Assuming that chlorine can be completely converted into iron(III)
chloride (FeCl a ) by passing the gas over heated iron, calculate what volume
of chlorine, measured at I7°C and 870 mm
pressure, would be required to
produce 32.5 g of iron(IH) chloride. (Fe = 56, CI = 35.5, 2 g of hydrogen
occupy 22.4 dm 8 at 0°C and 760 mmpressure.) (N.U.J.B.)
12. How would you obtain from common salt a concentrated solution
of hydrogen chloride?
Explain, giving equations, what takes place when the solution is treated
with (a) ammonia; (b) manganese dioxide; (c) iron(II) sulphide. (O. and C.)
13. (a) Indicate the chemistry of on b process of manufacture of each of
the following: (i) calcium oxide; (ii) chlorine; (iii) bleaching powder. (A)
What takes place when carbon dioxide is passed into a suspension of
bleaching powder? (N.U.J.B.)
14. Describe how you would prepare and collect a small quantity of
 SULPHUR 389

5. In smaller quantities for the manufacture of dyes, fireworks,

sulphur compounds, such as carbon disulphide, CS t and ,

medicinally in ointments.

Occurrence
Chapter 29
Sulphur occurs:

1. In Louisiana and Texas, U.S.A., as free sulphur;

2. In petroleum gases, e.g., at Lacq, as hydrogen sulphide.
Sulphur
(For sulphur in periodicity, see p. 87) Extraction of sulphur
In America the deposits lie at a depth of about 160
with m
ground and
THE element, sulphur,
of sulphur', a
•flowers
is a yellow solid. It is usually sold as either deposits of limestone, clay and sand between the level

powder, or 'roll sulphur', cylindrical sticks. ' <— Not compressed air
[Molten Sulphur
Uses of sulphur r,
and n
r=-*-\ana' Water
The output of sulphur in the world today exceeds 32 million tonnes 'Super-heated voter
-{Super
170'C under
\afl7C
annually, about two-thirds of it being produced by the United States pressure
of America. This vast amount is used in the following ways:

1. For the manufacture of sulphuric acid (see p. 411).

2. For dusting vines to prevent the growth of certain kinds of
fungus.
3. In making calcium hydrogen sulphite, Ca(HSO )„ which is
s
used as a bleacher of wood-pulp in the manufacture of
paper.
4. For the vulcanisation of rubber, a process which
converts the
soft pliable rubber into the hard, tough substance of which SULPHUR
motor tyres and similar products are made. BEDS

Wc
rater*-, ',) Water
j t!r

Suk Sulphur

Air

Fio. 123.
Frasch sulphur pump.

sulphur by
the sulphur (Fig. 122). It is not necessary to mine the
sinking shafts as in the case of coal, for sulphur differs from coal
in

By utilising this property

having a fairly low melting-point (115°C).
the sulphur can be extracted, by a method invented by
Frasch,
cheaply, rapidly and in a high state of purity.
Fio. 122. hole about 30 cm in diameter is bored down through the clay,
A
American sulphur deposits. sand and limestone to the sulphur beds. This boring is lined with an
388
390 A NEW CERTIFICATE CHEMISTRY SULPHUR 391

iron pipe and, inside the pipe, is sunk a device called the sulphur The action of heat on sulphur with a plentiful supply of air
pump. It consists of three concentric tubes which terminate in a Plunge a deflagrating spoon containing burning sulphur into a gas-
reservoir of larger diameter (see Fig. 123). Down the outermost of 1
the jar of air. The sulphur burns with a blue flame and leaves a misty
three tubes is forced a stream of water at about 170°C. This water
gas.
must be kept at a pressure of about 10 atm per square inch to main- way and use them for the following
Treat several gas-jars in this
tain it in the liquid state, i.e., it is super-heated water, and
it is hot tests:
enough to melt the sulphur. The molten sulphur flows into the
reservoir at the base of the pump and is forced up to the surface Add blue litmus solution.
through the second of the three tubes by means of a blast of hot It is turned red. The gas is an acidic oxide.

compressed air at a pressure of about 15 atm., which is forced down Add a dilute (pink) solution of potassium permanganate.
the narrowest tube. The sulphur is run into large tanks, where it It is turned colourless.
solidifies and can be separated from the water. Sulphur more
than
Add a dilute (golden yellow) solution of potassium dichromate.
99% pure is produced by this operation and a single pump may It is turned green.
produce up to 500 tons of this high-grade sulphur daily. sulphur dioxide (see
The results of these tests prove that the gas is
Sulphur from petroleum gases. At Lacq (S. France), gas associated
p. 403). Sulphur burns in air, forming sulphur dioxide.
with petroleum deposits contains mainly methane, CH«, with carbon
dioxide and hydrogen sulphide (15%). It is passed, at 70 atm pres- S + 0,->-SO a
sure, over an (alkaline) amine solution, which absorbs the
acidic
carbon dioxide and hydrogen sulphide. These gases are then released Formation of sulphides from sulphur
by heating at atmospheric pressure. Controlled supplies of air are
Sulphur will combine directly with many elements forming sul-
added and the hydrogen sulphide is oxidised to sulphur in three
phides. For example, if a finely ground mixture of iron filings and
stages, the last two in contact with a heated catalyst, bauxite.
sulphur, in the proportions of 56 to 32 by weight (Fe 56; S 32), = =
2H a S + 0,->2H O + 2S
t is heated, the two elements will combine vigorously and the whole

The sulphur vapour is condensed and then cooled to solid. The mass will glow spontaneously when once the combination has been
product is 99.9% pure. The deposits have been worked since 1957 started at one point. A black, or dark grey, residue of iron(lI)
and present yield is about 1.4 million tonnes per annum. sulphide is left.

Fe + S -v FeS
(iron(II)
The action of heat on sulphur when air is excluded sulphide)
Place some powdered roll sulphur in a narrow test-tube and
Hot copper foil or wire will similarly glow in sulphur vapour, forming
warm it gently, shaking well. Try to avoid local over-heating by rotat- copper(I) sulphide, Cu.S.
ing the test-tube. The sulphur passes through the following stages as 2Cu + S —> Cu,S
the temperature rises: form the important liquid,
Carbon combines directly with sulphur to

melts carbon disulphide, CS,.

1. It at about 115°C to an amber-coloured, mobile
C + 2S->CS,
liquid.
becomes much darker in colour and, suddenly, at 160°C, A very high temperature is required to bring about the combination, and
2. It
this is secured by means of the electric furnace, in which an
electric arc is
very viscous. So viscous does it become that the test-tube may struck between carbon electrodes and raises coke to white heat.
Sulphur is
white-hot
be inverted without loss of sulphur. also fed into the furnace. It vaporises and combines with the
3. The sulphur gradually becomes more mobile again and very coke. Carbon disulphide vapour passes off and is condensed.
dark reddish brown in colour. Carbon disulphide is poisonous and may be used to destroy low and
or
harmful forms of life, such as grain weevils (which feed on stored grain)
4. The sulphur boils at 444°C, giving off light brown sulphur cockroaches. It is very inflammable, and must be used with care. It is also
vapour. an excellent solvent. (See also CC1,, p. 297.)
These changes occur in the reverse order as the sulphur cools. 1
The misty effect is due to traces of sulphur trioxide formed simultaneously.
 392 A NEW CERTIFICATE CHEMISTRY SULPHUR 393

Action of adds on sulphur flame for the heating or the sulphur

i
Dilute acids do not act upon sulphur. It is oxidised by hot con- may begin to burn. Then allow
centrated sulphuric acid with formation of sulphur dioxide. the sulphur to cool. After a time,
a solid crust will begin to form
S + 2H,SO, -»- 3SO» + 2H sO on the surface. When the crust is
In this reaction the
sulphur is oxidised by the acid to sulphur continuous, pierce it at two widely
dioxide and the acid is reduced to the same substance. Of the three separated points with a glass rod
molecules of sulphur dioxide in the equation, one is the product of and rapidly pour out the liquid
oxidation of sulphur and two are the products of reduction of the sulphur from inside. With a pen-
sulphuric acid. The action is too slow to have practical value. knife, cut through the solid crust
Sulphur oxidised by hot concentrated nitric acid, with bromine
is all the way round the crucible or
Single crystal
as the best catalyst, to sulphuric acid. dish, near the rim, and lift it out. (simplified).
long
S + 6HNO3 -» H a SO« + 6NO, + 2H tO Underneath will be seen
'needle-shaped' crystals of sulphur Fio. 125.
This reaction is fully discussed on p. 438.
whose shape is shown in Fig. 125. Monoclinic sulphur.
They are crystals of monoclinic
ALLOTROPES OF SULPHUR sulphur or prismatic sulphur or (i-sulphur.
Note that this variety crystallises in close contact with hot, molten
The following experiments show that sulphur exists in several sulphur.
different forms, called 'allotropes'.
The meaning of this term will be
considered more fully after the experiments have been described. Preparation of Amorphous Sulphur (8-sulphur)
This variety of sulphur may be prepared in several ways. One is to
Preparation of rhombic or octahedral sulphur (a-sulphur)
saturate distilled water with hydrogen sulphide and then expose the
Shake some powdered sulphur with carbon disulphide for some solution to the air. Sulphur is deposited as an almost white powder,
time in a test-tube. (Take care to extinguish all flames in the vicinity.) amorphous sulphur or b-sulphur.
Filter the contents of the test-tube into a dry beaker through a
2H.S + O t ->-2H O +
s 2S
dry filter-paper and funnel. Fasten a filter-paper
over the mouth of the beaker, pierce a few pin- A llotropy and allotropes
holes in it, and set the beaker aside. The carbon In the experiment just described, we have prepared three different
disulphide will slowly evaporate, depositing varieties of the element sulphur. They have different properties, e.g.,
crystals of sulphur, which, because of the slow their densities (g/cm») differ (rhombic, 2.08; monoclinic, 1.98),
but
evaporation, will be large enough for their shape they all consist of pure sulphur and nothing else. When an element
to be seen. They will have the shape shown in can exist in several different forms in this way it is said to show
Fig. 124. allotropy. (See p. 287.)
This variety of sulphur is called rhombic sul-
Fio. 124. phur or octahedral sulphur or a-sulphur. Relation between monoclinic and rhombic sulphur
Crystal of rhombic Note especially that the formation of the The factor determining which of these two allotropes will be
obtained in an experiment is temperature. In our experiments, rhom-
sulphur crystals takes place at ordinary room tempera-
(simplified).
ture. bic sulphur was crystallised by evaporation of a solution of
sulphur
in carbon disulphide at ordinary room temperature, while
mono-
Preparation of monoclinic or prismatic sulphur clinic sulphur was crystallised in contact with a mass of hot, molten
(f3 -sulphur)
Place powdered sulphur in a very large crucible or an evaporating sulphur. Roughly, then, we may say that if the sulphur crystallises
dish. Heat it and stir, gradually adding more sulphur until the while still hot, it does so as the monoclinic allotrope; if it crystallises
!

crucible or dish is almost brim-full of molten sulphur. Use a small while cold, the rhombic allotrope is formed.
394 A NEW CERTIFICATE CHEMISTRY
We can go further. Experiment has shown that the temperature
which separates the two varieties is 96°C. If sulphur
crystallises
above this temperature, monoclinic crystals are formed, and if
below
it, rhombic. This temperature, 96°C
is therefore called the 'transition
temperature' between the two varieties.
If rhombic sulphur, stable below 96°C, is kept
Chapter 30
above that tem-
perature, it changes its crystalline form and becomes
monoclinic,
while, if monoclinic sulphur, stable above
96°C, is kept below that
temperature, it slowly yields rhombic sulphur.
Hydrogen Sulphide and the Sulphides
Formation of plastic sulphur
Heat some powdered roll sulphur in a test-tube until it is
boiling
rapidly. (The changes which occur are fully considered on
p. 390.)
HYDROGEN SULPHIDE, H,S
Then pour the boiling sulphur in a thin continuous stream into (also called Sulphuretted Hydrogen)
a
beaker full of cold water. It forms long, elastic, light-yellow
ribbons
of 'plastic sulphur', which are insoluble in carbon Preparation
disulphide. This
variety not a true allotrope of sulphur. If kept for a
is
few days, HYDROGEN sulphide was obtained in the experiment described

plastic sulphur becomes hard. This hard variety

of sulphur is in- on 7 by the action of dilute hydrochloric acid on ferrous sul-
p.
soluble in carbon disulphide. phide (iron(II) sulphide). This is the most convenient method of
preparation, using the apparatus shown in Fig. 126.
Comparison of two alio tropes of sulphur
..cone, hydrochtoric
Rhombic (octahedral) Monoclinic (prismatic) z acid

Yellow translucent crystals. Transparent amber crystals. hydrogen

Density 2.08 g/cm8 . Density 1.98 g/cm a . sulphide
Melting-point 114°C. Melting-point 119°C.
Stable at temperatures below Unstable at temperatures below
96°C. iron (n) sulphide^ Warm water
96°C, reverting to rhombic
variety. and water

Experimental evidence of the chemical identity of these allotropes

is
given by the fact that each is convertible into the other (by
tempera-
ture change) without change of weight and, if equal weights
of the Fig. 126.
allotropes are converted into a given compound
(e.g., sulphur
Preparation of hydrogen sulphide.
dioxide), identical weights of product are given.

If required to prepare the gas starting from sulphur, the best

it is

way to prepare iron(H) sulphide first by the method of p. 7 and

is
Questions on sulphur will be found on page 421.
then to use it in the way about to be described.
As the acid reaches the iron(II) sulphide, effervescence begins and
the hydrogen sulphide is collected over water. It is rather soluble in
cold water (about three volumes of the gas in one volume of water),
but like all gases, it is less soluble in hot water.
FeS(c) + 2HCl(aq)-»- FeCl.(aq) + H,S(g)
395
 396 A NEW CBRT1FICATB CHBMISTRY HYDROGEN SULPHIDE 397

Dilute sulphuric acid may also be used. Though very poisonous, the gas gives ample warning of its

FeS(c) + H,SO«(aq)-»- FeS0 4 (aq) + H sS(g) presence by its powerful smell.

Solubility in water. Invert a gas-jar of hydrogen sulphide in cold
Characteristic Test. Soak a of filter-paper in lead The rise of the water shows
strip water, remove the cover and shake gently.
acetate solution and drop it
into a gas-jar of hydrogen that the gas is fairly soluble. At ordinary temperatures, one volume
sulphide. The paper turns dark brown or black. This
of water can dissolve about three volumes of hydrogen sulphide.
colour change is caused by precipitation of black lead(Il)
To the solution in the gas-jar, add blue litmus solution. It is turned
sulphide.
claret colour. The solution is weakly acidic. It is known as hydro-
PKQHaOOs + H a S -> PbS| + 2C.H40, sulphuric acid, but the name is very seldom used. It is one of the
A purer specimen of hydrogen sulphide may be obtained by weakest acids known. Hydrogen sulphide is contained in the water
warm- of the sulphur springs round which have grown such spas as Harro-
ing antimony sulphide with concentrated hydrochloric acid.
gate. These 'waters' are said to have curative properties. They
6HC1 -> 2SbCI 3 + 3H aS
Sb 2 S s + certainly possess, as a consequence of their hydrogen sulphide
Tf required dry, the gas may be dried by passing it
over calcium content, all the unpleasant taste usually associated with medicines!
chloride and collected by downward delivery, as the gas is
somewhat Density. The gas has a density of 17 compared with that of hydro-
denser than the air. gen, and is somewhat denser than air, which is 14.4 times denser than
hydrogen.
Kipp's apparatus
Kipp's apparatus is a device for Combustion of hydrogen sulphide with a plentiful supply of air
obtaining intermittent supplies of a
When several gas-jars of hydrogen sulphide have been collected
frequently used gas such as hydrogen,
remove the delivery-tube and fix the tube as shown below (Fig. 128).
carbon dioxide or hydrogen sulphide.
Apply a lighted taper. The hydro-
(See Fig. 127).
gen sulphide burns with a blue Hydrogen
When the tap A
is opened, the
flame similar to that of sulphur. Sulphide
acid rises into the bulb B and attacks
Lower the tube into a wide gas-jar,
the ferrous sulphide, producing hydro-
closing the mouth with a square of
gen sulphide, which is delivered cardboard and, when the flame is
through A. When the gas is no extinguished, remove the tube and
longer required, A is turned off. The add a weak, pink solution of acidi-
gas is still being generated which
ferrous Sulphlda fied potassium permanganate. On
raises the pressure in B. The acid is
shaking, the solution becomes
therefore forced out of B and up into
colourless and remains This
clear. Fio. 128.
C. The generation of hydrogen sul- Combustion of hydrogen sulphide
test proves the presence of sulphur
phide now stops because acid and in a plentiful supply of air.
dioxide.
ferrous sulphide are no longer in con-
tact and the apparatus will remain
2H.S + 30. -* 2H4 + 2SO a

Fio. 127. inactive until tap A is again opened to

Kipp's apparatus.
obtain gas. Combustion of hydrogen sulphide with a limited supply of air
Cut down the air supply to the flame obtained in the last section by
Properties
putting into it a crucible lid.
Appearance. The gas is colourless. After a few seconds, a yellow deposit of sulphur will be seen on the
Smell. Hydrogen sulphide has a repulsive, rather
sweet smell lid. The reduced oxygen supply cannot
oxidise the gas completely
similar to that of a rotten egg. It is, in fact, deposited.
given off from putrefying and free sulphur is
eggs and also from decaying cabbages, both of which ->
contain sulphur. 2H 2 S(g) + 0,(g) 2S(c) + 2H a 0(l)
398 A NEW CERTIFICATE CHEMISTRY HYDROGEN SULPHIDB 399
Hydrogen sulphide as a reducing agent reduced by the gas. The effect diners from that produced by sulphur
Hydrogen sulphide a powerful reducing agent as the following
is dioxide because, while either gas decolorises the permanganate and
experiments show. Like all reducing agents, it operates as a supplier turns the dichromate from yellow to green, hydrogen sulphide leaves
of electrons. The usual product is a precipitate of sulphur, arising also a precipitate of sulphur, while sulphur dioxide does not.
from the changes:
~ 2KMnO« + 5H,S + 3H 8 S0 4 -»- K 8 S0 4 + 2MnSO« + 8H 8 + 5S|
fH 8 S ^ 2H + S2 +
{' 2 -
is -*-S + 2e-
K 8 Cr 2 7 + 3H,S + 4H 8 SO«-*K 8 SO t +Cr 8 (S0 ) 3 +7H 80+3S| 4

For the action of hydrogen sulphide with sulphur dioxide, see

The electrons are accepted by the oxidising agent with which the
p. 406, and for its action with the halogen elements, pp. 361, 385.
hydrogen sulphide is reacting. (Very powerful oxidation, e.g., by
concentrated nitric acid, may convert hydrogen sulphide to sulphuric
The action of hydrogen sulphide on salts of metals
acid.)
Action of hydrogen sulphide with nitric acid. Dilute some con- Copper{II) sulphate. Heat a solution of copper sulphate in a boiling-
centrated nitric acid with about one-third of its volume of water in a tube and pass hydrogen sulphide into it. A
dark brown precipitate
boiling-tube and pass hydrogen sulphide into it. Brown fumes of appears, copper(II) sulphide. Filter the mixture. If sufficient hydrogen
nitrogen dioxide are given off, a pale yellow deposit of sulphur sulphide has been passed, the filtrate will be colourless because all the
appears, and the liquid becomes hot. The hydrogen sulphide has copper, which formerly coloured it, is now precipitated as copper(II)
reduced the nitric acid to nitrogen dioxide and has sulphide. The filtrate is dilute sulphuric acid.
itself been
oxidised to sulphur. CuS0 4 + H 8S -> CuS + H 8 SO«
copper(II)
2HNO a + H 2S
->• 2H 8 + 2NO + S a j. sulphide
The solution also contains sulphuric acid, produced by the reaction:
Lead{ll) nitrate. Experiment as above.
H 8 S + 8HNO3 -» H S0 + 8NO a + 4H
8 4 8
Here, a black precipitate of Iead(II) sulphide is produced and the
Action of hydrogen sulphide with iron(III) chloride solution. Per- filtrate is dilute nitric acid.

form the experiment as above, using iron(III) chloride solution. Pb(NO s), +H 8 S - PbS + 2HNO,
A yellow deposit of sulphur appears and, on heating to coagulate Zinc sulphate. Experiment as above.
the sulphur and a pale green solution of iron(II) chloride is
filtering,
obtained. The hydrogen sulphide has reduced
A white precipitate of zinc sulphide is left and the filtrate contains
the yellow iron(IIT) dilute sulphuric acid.
chloride to green iron(Il) chloride, being itself oxidised to hydrogen
chloride, which dissolves in the water, and sulphur.
ZnS0 4 + H 8S - ZnS + H SO« 8

examples of double decomposition (see p. 160).

2FeCl 3 + H S -> 2FeCl + 2HCI + S
8 8
These reactions are all

or 2Fe!+ + S a - —* 2Fe 2f + SJ Hydrogen sulphide as an acid

Action of air on hydrogen sulphide. Pass a stream of hydrogen
sulphide into distilled water in a beaker for about half an hour. Leave Hydrogen sulphide acts as a weak dibasic acid. It forms with
the solution exposed to air. After a few days a white deposit sodium hydroxide two salts, normal sodium sulphide, Na 8 S,
of
amorphous sulphur will have appeared. The oxygen of the air has 2NaOH + H 8S -> Na 8 S + 2H 8
oxidised the hydrogen sulphide to sulphur and water. or, with excess of hydrogen sulphide, the acid salt, sodium hydrogen
2H8 S + 8 ->-2H 8 + 2S sulphide, NaHS.
Hydrogen sulphide will reduce concentrated sulphuric acid, NaOH + H 8 S -* NaHS + H t O
depositing sulphur. For this reason, the acid cannot be used to Potassium hydroxide reacts similarly.
dry
it.
With aqueous ammonia, the gas gives yellow ammonium sulphide,
3H 8 S + H„S0 4 -> 4H tO -f- 4S mainly NH
4 HS. This compound is used in
qualitative analysis.
Acidified potassium permanganate and dichromate solutions are NH 4OH + H S -* NH HS + H Q
8 4 8
 400 A NBW CERTIFICATE CHEMISTRY SULPHIDES 401

Laboratory preparation of sodium sulphide Formula of hydrogen sulphide

The possible reactions of hydrogen sulphide with sodium hydroxide This is considered on p. 1 19.
solution are:
2NaOH + H,S —* Na a S + 2H.O
2NaOH + 2H.S — 2NaHS + 2H.O
»• SULPHIDES
It is clear, from the equations, that the volume of hydrogen sulphide
needed to convert a given weight of sodium hydroxide into sodium hydro- K YSulphides of these metals
gen sulphide, NaHS, is twice that required to convert it to sodium sulphide, Na fare soluble in water.
Na 3 S. It is impossible in practice to determine when just enough hydrogen Sulphides of these metals will
sulphide has been used to convert the alkali into sodium sulphide, so the
best way of carrying out the preparation is to convert half of the sodium Ca [not precipitate from acidified

hydroxide into sodium hydrogen sulphide by saturation with hydrogen Mg solutions.

sulphide, and then to form the normal salt from the acid salt by addition Sulphides of these metals
Zn
of the other half of the sodium hydroxide.
Fe are insoluble in water. Sulphides of these metals will
NaOH + H,S -> NaHS + H.O Pb
NaHS + NaOH —> Na,S + H.O \precipitate from acidified solu-

Experiment. Measure out 50cm'of bench(about 2 M) sodium hydroxide

Ca tions.
it into two equal parts and, into one of them, pass hydrogen
solution, divide
sulphide until no more is absorbed and the liquid smells strongly of Potassium sulphide, K 2S
hydrogen sulphide. Add the other half of the sodium hydroxide solution sodium sulphide and is similarly prepared.
This is similar to
and obtain crystals of sodium sulphide by the method described on p. 230.
Sodium sulphide, Na,S
tytfagm
The preparation of this compound by neutralisation of sodium
hydroxide by hydrogen sulphide is described on p. 400. Its aqueous

P Piece of Lead
Acetate paper
is blackened
solution is alkaline and smells of hydrogen sulphide. When
with sulphur it forms 'poly sulphides' of sodium.

In industry, sodium sulphide

Na 2 S
For
+ 4S-*Na
is
heated
example:

2S B

prepared by heating sodium

- \ Boiling
Su/phur
sulphate with coke (p. 418).

Uses. (1) For preparing a class of very 'fast' dyes.

If (2) For stripping the hair from hides.

Calcium sulphide, CaS

Fio. 129.
Proof of composition of hydrogen sulphide. This compound was chiefly important in the form of the 'alkali
waste' of the Leblanc process. Sulphur was recovered from it.
If it contains traces of certain metals, for example, 0.01
bismuth, %
Proof that hydrogen sulphide contains only hydrogen and sulphur emit a
it is 'phosphorescent', that is, after exposure to light,
it will
Heat sulphur in a boiling-tube till it is boiling, then pass violet glow whose intensity gradually diminishes. The glow fades out
through it a
stream of dry hydrogen by apparatus shown in
Fig. 129. The wet lead after some hours.
acetate paper will be turned black. This proves
that hydrogen sulphide is
present in the gases. Since it can only have
been produced by direct cora-
bimuion of hydrogen and sulphur, it must contain
these two elements
Zinc sulphide, ZnS
This compound occurs as the mineral 'zinc blende'. It may be pre-
H, +S—*-H,S cipitated by hydrogen sulphide from a neutral (or alkaline)
solution
This is not a practical preparation of hydrogen sulphide.
Only a very small of a zinc salt. .
proportion of the hydrogen is converted to hydrogen sulphide.
Zn s+ + S»~ -» ZnS J
402 A NBW CERTIFICATE CHBMISTRY
Like calcium sulphide, and under similar conditions,
zinc sulphide
is phosphorescent. The luminous paint on watches is
usually zinc
sulphide, containing about 1 part of a radium salt
in 100 000 000 of
the sulphide.
Chapter 31
Iron(II) sulphide, FeS
This black, insoluble compound is usually employed
for the pre-
paration of hydrogen sulphide (p. 395). It is prepared
by heating iron
with sulphur in the calculated quantities Oxides and Acids of Sulphur
(p. 391).

Iron disulphide (iron pyrites), FeS

and the Sulphates
2

This occurs as a hard, brassy mineral. There are

great masses of it
in Spain. Itis the cheapest source of
sulphur dioxide, which it gives
off when burnt in air (p. 41 1). SULPHUR DIOXIDE
Preparation
Lead(II) sulphide, PbS
Lead (II) sulphide occurs as the mineral galena, THIS compound, which is a gas under ordinary conditions, is con-
and is precipitated veniently prepared in the laboratory by the apparatus of Fig. 130.
from solutions of lead salts by hydrogen sulphide
(p. 399). The most There is no action until the mixture in the flask becomes hot Then
satisfactory test for hydrogen sulphide
(p. 396) is the production of a rapid effervescence occurs and the sulphur dioxide, being very soluble
dark brown (almost black) stain of lead(II) sulphide
on a filter-paper in water and denser than air, is usually collected as shown. It may
soaked in lead(II) acetate solution.
also be collected over mercury.
Pb a+ + S 2 - ->- PbS | Cu(c) + 2H S0
8 4(1)
-»• CuS0 4 (c) + 2H,0 + SO t (g)

Copper(II) sulphide, CuS Concentrated

, Sulphuric
This is a black insoluble compound precipitated '
Acid
from a solution of
a copperfH) salt by hydrogen sulphide
(p. 399).

Cu»+ + S " -* CuS |

a

Questions on sulphides will be found on page

421.

Sulphur
'Dioxide

Cone. Sulphuric acid

to dry the gas
Fio. 130.
Preparation of sulphur dioxide.
403
404 A NEW CERTIFICATE CHEMISTRY SULPHUR DIOXIDE 405

A dark brown mixture is left in the flask. It contains anhydrous The following are important examples of the reducing action of sul-
copper(II) sulphate and certain impurities. Crystals of copper(II) phur dioxide in aqueous solution.
sulphate may be obtained from it by the method described on p. 231. (a) Action of sulphur dioxide with concentrated nitric acid. Put some
concentrated nitric acid into a boiling-tube and pass into it a current of
Tests. 1. The gas has a very irritating smell and a metallic
sulphur dioxide from a siphon of liquid sulphur dioxide. Brown fumes
taste.
are evolved (nitrogen dioxide) and the liquid becomes warm. Dilute
2. Action on potassium permanganate solution. The solu-
tion is turned from purple to colourless by sulphur dioxide.
some of the liquid and add dilute hydrochloric acid and barium chlor-
ide solution (the recognised test for a soluble sulphate). The white
(No precipitate as in the case of reduction of the per-
is left
precipitate of barium sulphate proves the presence of sulphuric acid.
manganate by hydrogen sulphide.)
5SO, + 2KMnO t + 2H a O -> K,S0 4 + 2MnS0 4 + 2H,S0 4 BaCl, +H 8S0 4 -»- BaS0 4 + 2HC1
The explanation of the change in colour is that the potassium The concentrated nitric acid has oxidised the sulphur dioxide in
permanganate is decomposed and all the products of the reaction the presence of water to sulphuric acid and has been itself reduced to
give colourless solutions. (The manganese sulphate is too small in nitrogen dioxide.
amount for its very pale pink colour to be observed.)
SO» + 2HN0 3 -»- H,,S0 4 + 2N0 2
Properties of sulphur dioxide
(b) Action of sulphur dioxide on iron(HI) sulphate solution. Make a
Appearance. The gas is colourless. solution of iron(III) sulphate (or iron ammonium alum) in water in a
Smell. The gas has an irritating smell and a rather sweet taste. It boiling-tube and pass into it sulphur dioxide as above. The brownish
fairly poisonous and is used for fumigation. colour of the solution is rapidly converted to pale green. The sulphur
1
is

Solubility in water. Invert a gas-jar of the gas in cold water and dioxide has reduced the brown iron(III) sulphate to light green
shake. The
rapid rise of water shows that the gas is readily soluble in iron(II) sulphate and has itself been oxidised to sulphuric acid.
water. Add to the liquid some blue litmus solution. It is turned red.
The solution is acidic.
2IV+ + 2H sO + S0 2
- 2Fe*+ + S0 4 °- + 4H +
The sulphur dioxide reacts chemically with the water to produce (c) Action of sulphur dioxide on potassium dichromate. Acidify a
sulphurous acid. solution of potassium dichromate in a boiling-tube with dilute sul-
H.O + SO a ?± H SOg *± 2H+ + S0 8«-
a
phuric acid, and pass through it a stream of sulphur dioxide from a

siphon of liquid sulphur dioxide. There is a rapid colour change from

This acid will be considered more fully later.
golden yellow to green, but no precipitate appears (compare the
action of hydrogen sulphide, p. 399).
Sulphur dioxide as a reducing agent
Sulphur dioxide, in the presence of water, is a powerful reducing K e Cr 2 7 + 3S0 3 + H 2 S0 4
- K S03 4 + Cr^SOJ, + H O t

agent. It reacts with water to form sulphurous acid and the sulphite The potassium dichromate has oxidised the sulphur dioxide in the
_
ion, S0 3 * , and this ion, like reducing agents in general, acts as a presence of water to sulphuric acid, being itself reduced to green
supplier of electrons. This occurs in association with water. chromium(III) sulphate.
H sO + SO, ^ H SO, ^ 2H + + S0 ~ 2 (d) Action of sulphur dioxide on potassium permanganate. (See test
+ H.O - S0 4»- + 2H+ + 2e~
2 3
SCy- for sulphur dioxide p. 404.)
The electrons are accepted by the oxidising agent with which the The potassium permanganate oxidised the sulphur dioxide in the
S0 2 -water system is reacting, e.g., presence of water to sulphuric acid, and was itself reduced to man-
ganese(II) sulphate.
iron(III) ion, which is reduced to iron(II) ion Fe 3+ + e~—*- Fe2+ :

chlorine, which is reduced to its ions: Cl a + 2e~ —* 2C1 - 5SO t + 2KMnO« + 2H O ->• K«S0 4 + 2MnS0 + 2H,S0 4
s 4
acidified potassium permanganate, which is reduced to a man-
ganese(II) salt: 1 The red solution which may be formed is a complex sulphite which de-

Mn0 4
" + 8H+ + 5e~ -* Mn* + + 4H O g
composes on heating, leaving the products as indicated by the equation above.
406 A NEW CERTIFICATE CHEMISTRY SULPHUROUS ACID 407

Bleaching action of sulphur dioxide Action oflead(lV) oxide on sulphur dioxide. Warm some lead(lV)
Sulphurous acid is a bleaching agent. This may easily be shown by oxide (lead dioxide) on a deflagrating spoon and lower it into a gas-
dropping into a gas-jar of the gas (containing some water) a few blue jar of sulphur dioxide. The lead dioxide glows and a white deposit of
flowers, e.g., blue crocus, lead(II) sulphate is left.
iris, or bluebells. After a few minutes, the
flowers will have lost their blue colour. Pb0 2 + SO t -*-PbS0 4
This bleaching is also a reducing action. The sulphurous acid takes
up oxygen from the colouring matter of the flowers and forms sul- Liquefaction of sulphur dioxide
phuric acid; the removal of oxygen from the dye converts it to a Sulphur dioxide can readily be liquefied by being dried by con-
colourless compound. Sulphur dioxide is used industrially for bleach- centrated sulphuric acid and passed through a freezing mixture of ice
ing sponges and straw for straw hats. The oxygen of the air may and salt. It liquefies under ordinary atmospheric pressure at about
oxidise the reduced colourless compound back to the original coloured — 10°C. It canbe kept liquid at ordinary room temperature if under
compound, which explains why straw hats gradually become yellow and it is sold in siphons under pressure.
slight pressure,
with use. Formula of sulphur dioxide. See p. 120.
Action of sulphur dioxide on halogen elements. See p. 363.
Sulphur dioxide in chemical industry
Action of sulphur dioxide with hydrogen sulphide
Sulphur dioxide is very important as an intermediate compound
Add a gas-jar of sulphur dioxide a little water, invert over it a
to
in themanufacture of sulphuric acid (p. 411). It is prepared by burn-
gas-jar of hydrogen sulphide and allow the gases to mix. A yellow
ing sulphur in air.
deposit of sulphur will be produced at once. The dry gases do not s + o,->so.
react.
or by burning iron pyrites in air.
2H 2 S + S0 8 -*-2H sO + 3S
Note that, here, the sulphur dioxide is actually acting as
an oxidising
4FeS i!
+ 110, -»• 2Fe t 3 + 8SO t

agent, supplying oxygen to the hydrogen sulphide. As we have seen

above, however, sulphur dioxide usually shows reducing properties.
Here it has encountered in hydrogen sulphide a more powerful
SULPHUROUS ACID, HjSOa
reducer than itself, which takes up its oxygen and causes it to act as This acid has never been obtained free from water. Any attempt to
an oxidiser. prepare the pure acid always results in its decomposition into sulphur
dioxide and water.
Gass experiments confirming properties of sulphur dioxide
It is prepared by passing sulphur dioxide into water. The
gas is
Put one or two grams of sodium sulphite crystals into a test-tube, readily soluble and it is advisable to prevent 'sucking back' by the
cover them with dilute hydrochloric acid and warm. Dip a clean glass use of a funnel just touching the water surface (Fig. 131).
tube into a very dilute solution of potassium permanganate and lower The reaction in the flask is the same as described under the pre-
it into the gas. Be careful not to lower it into the liquid or into the paration of sulphur dioxide (p. 403). It is, of course, not necessary
spray immediately above the liquid. The pink colour is discharged. here to dry the sulphur dioxide.
Remove the tube, wash well with water and repeat using the following: Cu + 2H,S0 4 -»- CuS0 4 + 2H tO + SO,
(a) potassium dichromate solution, SOt+HaO-^HjSOi,
(b) blue litmus solution, Sulphur dioxide is the anhydride of sulphurous acid and may be
(c) chlorine water, called 'sulphurous anhydride'.
(d) hydrogen sulphide water, Definition. An anhydride is the oxide of a non-metal, which, when com-
(e) barium chloride solution, bined with water, forms an acid.
8-
(/) barium chloride solution acidified with dilute hydrochloric
CO, + H,0 s» H,CO, ^ 2H+ + C0 3
acid. carbonic carbonic
anhydride acid
(Sec pages 404, 405, for explanations.)
408 A NEW CERTIFICATE CHEMISTRY SULPHUROUS ACID 409
SO, -|- H 2 ^H 2 SO s ^ 2H+ + S0 3»-
proves that the oxygen of the air has oxidised the sulphurous acid to
sulphurous sulphurous
anhydride acid
sulphuric acid.
2H 3 S0 3 + ->2H 2 S0 4
SO„ +H 2 ^H 2 S0 4 ^ 2H + + S0 4*- Ba"(aq) + S0 4
2
2
"(aq) -> BaS0 4(c)
sulphuric sulphuric
anhydride acid

An anhydride will not always combine directly with water to give the Action of sulphurous acid with alkalis
corresponding acid, e.g., silicon dioxide, Si0 2 , is the anhydride of Sulphurous acid is a dibasic acid and with sodium hydroxide forms
silicic acid, H 2 Si0 3,though the acid cannot be prepared by direct two sodium salts, the acid salt, sodium hydrogen sulphite, NaHS0 3 ,

and the normal salt, sodium sulphite, Na a S0 3 .

Concentrated NaOH + H 2 S0 3 -> NaHSO s + H s O

| j
Sulphuric
2NaOH + H 3 S0 3 -»- Na 2 S0 3 + 2H 2
Potassium hydroxide solution behaves similarly.
Laboratory preparation of sodium sulphite. This is similar to the
preparation of sodium sulphide, described on p. 400, using sulphur
dioxide instead of hydrogen sulphide.
NaOH + H 2 SO a ->- NaHS0 3 + H a O
NaHS0 3 + NaOH -* Na 2 S0 3 + H 2
Sulphites give off sulphur dioxide when warmed with dilute hydro-
chloric acid or dilute sulphuric acid (test for S0 2 , p. 404), e.g.,

Na 2SO a + H S0 -* Na 2SO« + H
2 4 2 + S0 2

This is occasionally used as a method of preparing sulphur dioxide.

Used in dilute acidified solutions, sulphites have all the reducing

actions of sulphur dioxide and water, or sulphurous acid (see p. 404).

Preparation of sulphurous acid, H S02 3,

from sulphur
Fio. 131.
Preparation of sulphurous acid. To convert sulphur into sulphurous acid it is necessary first to
oxidise the sulphur to sulphur dioxide and then absorb this gas in
water.
combination of its anhydride with water. The acid is prepared from
This can be done by the apparatus of Fig. 132.
one of its salts and, when heated, loses water, leaving silicon dioxide
as the residue.

Properties of sulphurous acid Air To filter

1^3_
Sulphurous acid is a colourless liquid which smells strongly of
sulphur dioxide. W Sulphur
Jj
Reducing action Water
(0 The acid has all the reducing actions described previously as
those of sulphur dioxide in the presence of water (pp. 404-5).
(ii) Effect of exposure to air. Leave a beaker of sulphurous acid

exposed to air for a few days. Then add to it hydrochloric acid and Fio. 132.
barium chloride solution. The white precipitate of barium sulphate Preparation of sulphurous acid from sulphur.
 410 A NEW CERTIFICATE CHEMISTRY SULPHURIC ACID 411
Heat the sulphur and, by means of a filter-pump, draw The platinum is a catalyst and the best temperature is 45O°-500°C.
over it a
rapid stream of air. The sulphur burns and the
sulphur dioxide pro- The sulphur trioxide is seen as dense white fumes and may be solidi-
duced is absorbed as it passes through the water in the and a common
WoulfTs fied in a freezing mixture of ice little salt (Fig. 133).
bottle. The liquid left is sulphurous acid. Sulphur
vapour may be 2S0 3 +0»-»-2S0 3
earned over unburnt and appear as a yellow precipitate
in the bottle.
Remove it by filtration. The sulphur trioxide container is protected from atmosphericmoisture
by a calcium chloride tube. Sulphur trioxide is important because it
S + 8 ->SO, combines vigorously with water, giving sulphuric acid.
H tO + S0 3 ->H 3 S0 8
The method of producing sulphurous H 3 + S0 3 -»-H a S0 4
acid given on p. 403 is much
more convenient in the laboratory, but the sulphurous acid It is the anhydride of this acid and sulphur trioxide may be termed
prepared
on the large scale is made by modification of the above method 'sulphuric anhydride'. (Sec also p. 408.)
or
by burning iron pyrites, FeS a .

4FeS 3 + HO, -»- 2Fe O s + 3 8SO,

SULPHURIC ACID
Lead chamber process for the manufacture of sulphuric acid
SULPHUR TRIOXIDE of the raw materials, sulphur and pyrites,
To offset Britain's lack
This compound is a white hygroscopic solid. A sample of it is a new process is producing sulphur dioxide by strongly heating
usually kept in a sealed glass bulb as a laboratory exhibit. anhydrite, CaS0 4 , with coke. The main reaction is:

2CaS0 4 + C -> 2CaO + 2SO, + CO a

Preparation of sulphur trioxide
By including sand and ashes containing alumina, the quicklime is
It is prepared by passing a mixture of dry sulphur dioxide and
dry converted to a valuable by-product, cement (calcium silicate and
air, or oxygen, over heated platinised asbestos (or vanadium aluminate). Pyrites is also burnt in air to produce sulphur dioxide.
pent-
oxide). Platinised asbestos ismade by soaking asbestos in platinum 4FeS a + 110 8 -*• 2Fe a 3 + 8S0 3
chloride solution and then igniting it, when platinum is left in a very
It is converted by the oxygen of the air, in the
presence of steam, into
finely divided form.
sulphuric acid. Nitrogen monoxide is used as a catalyst or oxygen-
PtCI 4 ->- 2C1, + Pt carrier.
2NO-f 3
->-2N0 3
from
air
platinised asbestos
(450°-500°C) N0 + H
2 3 + SO, -* NO + H S0 4 2

Wide tube The nitrogen monoxide is usually supplied in a modern plant by

ammonia by oxygen of the The two gases are passed
gal —-feT oxidising air.

m calcium
over heated platinum.
4NH 3 + 50 2 - 4NO + 6H
"S3 cone
sulphunic
Freezing
mixture chloride
The main oxidation of the sulphur dioxide is carried out in large lead
2

| (anhydrous)
acid to chambers, on the floors of which 'chamber-acid' (65% sulphuric
sulphur where an
dry the acid) accumulates. It is not very pure but finds a ready sale
gases trioxide
acid of high purity is not needed. The plant used is made more
elaborate by devices for recovery of the nitrogen monoxide, which
Fig. 133. would otherwise escape, and for its restoration into the reacting
Preparation of sulphur trioxide. gases.
 412 A NEW CERTIFICATE CHEMISTRY SULPHURIC ACID 413

Contact process for manufacture of sulphuric acid (see also

2NaOH + H,S04 —»-Na,S0 4 + 2H.O
p. 157)
Then measure out a further 00 cm 3 of the same sodium hydroxide solution
1

Sulphur dioxide (prepared by burning sulphur) and air are passed

and add to it, from the burette, 2x cm" of the same acid. This solution now
oyer a catalyst, heated to 450°-500°C. About 98% of the possible contains sodium hydrogen sulphate.
yield of sulphur trioxide is obtained.
2NaOH + 2H.SO, -> 2NaHS0 4 + 2H,0
2SO t + O t ^ 2SO, Obtain crystals in the usual way from both solutions (see p. 231).
Originally, platinised asbestos was used as catalyst but platinum is Similarly, two potassium salts, potassium sulphate, K,S04 and potas- ,

very expensive and easily 'poisoned' by impurity which made elabor- sium hydrogen sulphate, KHS0 4 can be made. ,

ate purification of the gases necessary (especially from arsenical Dilute sulphuric acid also neutralises basic oxides or hydroxides
com-
pounds). Vanadium pentoxide, V 2 5 has replaced platinum as the to form salts and water, e.g.,
usual catalyst employed.
,

CuO + H 2 S0 - CuS0 + H,0

The sulphur trioxide
A mist of fine drops of dilute
cannot be satisfactorily absorbed by water. ZnO +H
S0 4 2
4
-
ZnS0 4 + H 2
4

sulphuric acid fills the factory if direct Cu(OH) 2 + H 2S0 4 -> CuS0 4 + 2H 2
absorption in water is tried. It is dissolved in concentrated sulphuric Zn(OH) a + H 2 S0 4 -»• ZnS0 4 + 2H 2
acid, forming a fuming liquid called 'oleum' for which there is some
Action of dilute sulphuric acid with metals. Some of the common
demand. Most of the 'oleum' is carefully diluted with the correct
metals displace hydrogen from dilute sulphuric acid, e.g.,
amount of water to give ordinary concentrated sulphuric acid.
SO a + H 2 -»- H S0 4
Zn + 2H+ +H
-»- Zn 2+ g
2
Fe + 2H + -»-Fe 4+ -r-H 2

Properties of sulphuric acid Mg + 2H+ -»• Mga+ + H»

Sulphuric acid is a dense oily liquid, 'Oil of Vitriol'. It has several Copper is, however, without action on this acid. Note that cold,
very important properties. concentrated sulphuric acid, in the complete absence of water, is not
attacked by any metal.
Dilute sulphuric acid — as an acid Action of sulphuric acid with carbonates. If the sulphate of a metal
Sulphuric acid is dibasic, ionising in two stages to produce first a is soluble, dilute sulphuric acid readily attacks its carbonate with
hydrogen ion and a bisulphate or hydrogen sulphate ion, HS0 - from evolution of carbon dioxide, e.g.,
4 ,

a molecule of the acid, after which the bisulphate ion may ionise
Na t CO s + H S0 -> Na S0 4 + H gO + CO
further to produce a hydrogen ion and the sulphate ion, S0 2 ~
H S0 4 ^ H+ + HS0 4 - ^ 2H + + S0 4 2~
4 MgCOa + H,S0
2 4

4
-
MgS0 4 + H + CO,
2

2
a

2 or CO s - + 2H + -> H O + C0
a
a 2
In dilute solution, the acid is almost completely ionised and so a CaCO s however, the
added to marble,
is If dilute sulphuric acid is ,

strong acid. checked after a few seconds. This is because the

effervescence is
Because of its dibasic character, this acid forms two sodium salts,
calcium sulphate which is formed is only sparingly soluble in water
sodium sulphate, (Na') 2 S0 4 2 -, and sodium hydrogen sulphate or
and soon forms a deposit on the surface of the marble, separating it
sodium bisulphate, Na + HS0 4 - .
from the acid and checking the action.
2(Na+OH-) + (H+) a S0 4*~ -»- (Na+) 2 S0 42 - + 2H g O
Na'OH- + (H+) 2 S0 4 s - ->- Na + HS0 4 " + H 2 Concentrated sulphuric acid as an oxidising agent
Preparation of sodium sulphate and hydrogen sulphate. It is evident from Like all oxidising agents, sulphuric acid acts as an acceptor of
the previous equations that the amount of sodium hydroxide needed to electrons. When hot and concentrated, the acid shows, as its principal
convert a given amount of sulphuric acid into sodium hydrogen sulphate is
reaction:
half that required to convert it to sodium sulphate.
Measure out, say, 100 cm" of bench (2 M) sodium hydroxide solution 2H 2 S0 4 + 2e~ -»• S0 4*- + 2H sO + SO,
into a flask, add litmus and then run in carefully, from a burette,
bench The electrons are supplied by the reducing agent concerned in the
(2 M) dilute sulphuric acid, until the solution is neutral (purple). Note the
volume of dilute sulphuric acid needed (say x cm*). This solution now reaction. This may be a metal, such as copper or zinc:
contains sodium sulphate.
Cu (or Zn) -> Cu2+ (or Zn 2 -) + 2e~
414 A NEW CERTIFICATE CHEMISTRY SULPHURIC ACID 415
2_
The metallic ion is left associated with the S0 4 ion as the correspond-
Concentrated sulphuric acid as a dehydrating agent
ing metallic sulphate, and the reaction is usually written in a single
equation, as: 1. With sugar.
Place about a tablespoonful of sugar in a 450
cm 3 beaker and cover
Cu (or Zn) + 2H S0 -* CuS0 4 (or ZnS0 4)
2 4 -j- 2H gO + SO, it with water. Place
the beaker in a trough, for safety, and pour in a
The non-metals, carbon and sulphur, are also oxidised by the hot, steady stream of concentrated sulphuric acid. The sugar is charred
concentrated acid to give sulphur dioxide or carbon dioxide. spongy black mass of charcoal rises, filling the beaker. Steam
and a
S + 2H,S0 4 -* 2H 2 + 3S0 is given off and the whole
mass becomes very hot.
2
C + 2H 2 S0 4 -* 2H 2 + 2S0 + C0 The acid hastaken out the elements of water from the sugar leaving
2 2

The sulphur dioxide given off may be detected by the decolorisa- a black mass of carbon.
tion of potassium permanganate solution. C„H mO„ (+ «H 2SO«)->. 12C + (11H 2 + nUJOJ
A similar actionthe explanation of the very marked corrosive
is

Concentrated sulphuric acid possesses an affinity for water action of the acid on cloth, e.g., cotton.
This is cellulose, whose

The
acid has a very great affinity for water. It mixes with water simplest formula is C 4H 10O 6 As above,
.

with a very great evolution of heat. The two, when mixed in equal C,H 10O (+ «H 2 S0 4)
5
- 6C + (5H 2 + nH 2 SO«)
volumes at room temperature, may give a liquid whose temperature reactions account for its
is as high as 120°C. This indicates chemical reaction but its nature is and a hole appears in the cloth. Similar
rapid and serious burning of the skin.
not clearly understood. It is very important when mixing the acid with
water to add the acid to the water and NEVER the water to the acid. 2. With oxalic acid, H 2C 2 4.

Place a oxalic acid in a test-tube, add a little concentrated

little
It is necessary to stir the liquid as the acid enters to prevent formation
occurs. Apply a lighted
of a lower layer of acid. sulphuric acid and warm gently. Effervescence
test-tube. The gas burns with a blue flame, showing that
Concentrated sulphuric acid is hygroscopic, i.e., it absorbs water- splint to the
is given off. Extinguish the flame and pass the gas
vapour out of the air, increasing in bulk and becoming dilute. This carbon monoxide
into lime-water held in a boiling-tube.
The turbidity shows that
present. The reaction is of the same type as
carbon dioxide is also
Concentrated Now those above, and it is used for the laboratory preparation of carbon
Sulphuric di/uUd monoxide
acid \^ in==.V:
(see p. 299).

??.:—"•
H 2C 2 4 (+ H 2S04) -> CO + CO, + (H O + a H.SOJ

Exposure lo air After exposure to air

just beginning. for about three weeks. Uses of sulphuric acid
sulphuric acid the United
In quantitative order, the uses of
in
Fio. 134.
Exposure of concentrated sulphuric acid to the air.
Kingdom (1968) were as given below.
such as ammonium sulphate and calcium
34% for fertilisers,
can be shown by the following experiment for which Fig. 134 is superphosphate;
sufficient explanation. The concentrated acid is used for drying gases, in the manufacture of paints and
pigments;
15%
e.g., sulphur dioxide, chlorine, hydrogen chloride. It cannot be used 13% in connection with natural and man-made fibres;

to dry a reducing gas like hydrogen sulphide, or an alkaline gas like for the production of other chemicals,
such as metallic sul-
12%
phates, hydrochloric acid, hydrofluoric acid and
ammonia. plastics;

So great is the affinity of concentrated sulphuric acid for water that 9% in the manufacture of detergents and soap;
it can decompose many compounds by removing from them the in connection with the extraction and
use of metals, in-
4%
hydrogen and oxygen necessary to form water, with which it then cluding 'pickling' to clean metallic surfaces.
combines. This is called a dehydrating action.
The remaining 13% covered various minor uses.
416 A NEW CERTIFICATE CHEMISTRY SULPHATES 417

Test for sulphuric acid and soluble sulphates. To a little acid in slight excess to counter hydrolysis. The sulphate can be ob-
dilute sulphuric acid in a boiling-tube add dilute hydro- tained by evaporation to small bulk and cooling, but it does not
chloric acid and barium chloride solution. A white precipi- crystallise well.
tate of barium sulphate is formed. This is the characteristic
test for any soluble sulphate.
2A1(0H) 3 + 3H S0 -> AIjCSOJs + 6H aO
2 4

It ismost commonly encountered in the form of potash alum, one

BaCl a + H S0 2 4
-»- 2HC1 + BaSO« J of an important group of salts called the alums.

The alums
SULPHATES
These are double salts of general formula
Methods of preparation
These are fully dealt with in the chapter, 'Acids, Bases and
X,S0 4 .Y a (S0 4) 3 .24H 2 or X + Y» + (S(V-) 2 .12HaO
Salts',
pp. 222-37. Briefly summarised, they arc where X is Na, K or 4 NH
and Y is Fe(IU), Al or Cr. 1
(1) By the action of sulphuric acid on a metal.
Dilute acid
(Note that X is a monovalent and Ya /r/valent metal.)
The alums crystallise well from water. They all have similar crystal-
Fe + H 2S0 4
->• FeS0 4 + H, line shape, consequently crystalline layers of different alums may be
iron(Il)
sulphate
deposited on one another to produce large, composite crystals with
layers of varying colours.
Mg + H S0 2 4
-»- MgS0 4 + H,
magnesium The two commonest alums are:
sulphate

Zn + H S0 -> ZnSO« + H, Potash alum K S0 2 4 .A1 2 (S04),.24H,0 (colourless)

s 4
zinc Iron(III) alum (NH 4 ) 2 S0 4 .Fe t (S0 4) 3 .24H 2 (purple)
sulphate

Hot concentrated acid Preparation of potash alum

Cu + 2H S0 -* CuS0 + 2H 2 +
2 4 4 SO, (This is commonly called simply 'alum'). Potassium sulphate and

By aluminium sulphate are weighed out approximately in the propor-

(2) the action of dilute sulphuric acid on the oxide, hydroxide or
carbonate of the metal. tions of their molecular weights

For example: + H S0 4
CuO 2 CuS0 4 + H 2 K S0
2 4 : A1 1(S04),.18H 1
174 g 666 g
Zn(OH) + H S02 2 4 ZnS0 4 + 2H sO
Na C0 + H S0 Use, say, one-twentieth of these figures, i.e., 8.7 g and 33 g. These
2 3 2 4 Na 2 S0 4 + H aO + C0 2
sodium amounts are dissolved, with heat, in as little water as possible. In the
sulphate case of the aluminium salt, the water should be slightly acidified with
By
double decomposition dilute sulphuric acid. The hot solutions are then mixed and stirred.
(3)
This limited in application to the preparation of insoluble sul-
is On cooling, colourless alum crystals separate out and are filtered,
phates. Only two common sulphates are insoluble, barium sulphate washed with cold distilled water and dried.
and lead sulphate. (Calcium sulphate is sparingly soluble.)
Ammonium sulphate (sulphate of ammonia), (NH 4 ) 2S0 4
Pb ,+ (aq) + S0 4 z -(aq)-* PbS0 (c) 4
This compound is very widely used as a nitrogenous fertiliser. It
Ba*+(aq) + S0 4 *-(aq) -* BaS0 4(c)
may be made in the laboratory by neutralisation of dilute sulphuric
Aluminium sulphate, Al.,(S0 1 ) 3 .18H..O acid with ammonia (p. 234). In industry, it is produced by the action
This is a white solid. It is conveniently prepared by dissolving the
oxide or hydroxide of the metal in dilute sulphuric acid, leaving the
1 Alums are also formed from some less common metals, for example caesium
and rubidium.
418 A NEW CERTIFICATE CHEMISTRY SULPHATES 419

of ammonia and carbon dioxide on the mineral 'anhydrite', calcium Magnesium sulphate, MgS0 4
sulphate, in the presence of hot water.
Magnesium sulphate heptahydrate, MgS0 4 .7H a O, is the familiar
CaS0 4 + 2NH 3 + CO + H O ->- CaC0 substance, 'Epsom salt'. It occurs in springs at
Epsom and Bath and
a a 3 j + (NH 4) 2 S0 4
The chalk is filtered off and the ammonium sulphate crystallised. is usually prepared from the mineral, kieserite, 4 .H 20, found MgS0
at Stassfurt. It acts as a mild purgative.
the method described on
Potassium sulphate, K.S0 4 In the laboratory it may be prepared by
p. 230.
This compound may be prepared in the laboratory by neutralisa-
tion of potassium hydroxide solution by dilute sulphuric acid
(p. 234).
Zinc sulphate, ZnS0 4
In industry, it is usually prepared by heating potassium chloride with This encountered as the heptahydrate, ZnS0 4 .7H aO,
salt is usually
laboratory from zinc, zinc
concentrated sulphuric acid. 'white vitriol'. It can be prepared in the
and preparation is fully described on
2KCI(c) + H SO -» K 2 S0 4 (c) + 2HCI(g) oxide or zinc carbonate, its
8 4 0)

Unlike most soluble sulphates, crystallises without water of crystal- in 100 g

transparent crystals are very soluble in water (138 g
it
Its
lisation. the treatment
water at 10°C) and the salt is used as an emetic and for

of certain skin diseases.

Sodium sulphate, Na.SO.,

This met with in the form of transparent crystals of

salt is usually
IronfEl) sulphate, FeS0 4
is known as 'green
the decahydrate, Na 2 SO 4 .10H 2 O, Glauber's salt. In the laboratory, Iron(II) sulphate heptahydrate, FeS0 4 .7H 2 0,
the laboratory by the action of iron
it may be made by neutralising sodium hydroxide vitriol'. It is usually prepared in
solution by dilute
or borings) on dilute sulphuric acid (p. 230).
sulphuric acid (p. 234). In industry, it is prepared by heating sodium (wire, filings
of air and water on the
chloride with concentrated sulphuric acid. In industry, it is obtained by the action
It is used in medicine, in the manufacture of glass, and, mineral, iron pyrites, FeS..
by heating
with coke, for the manufacture of sodium sulphide. 2FeS a + 70 a + 2H 2
-* 2FeS0 4 + 2H 2 S0 4
neutralised by scrap iron and the iron(II) sul-
Na,S0 4 + 4C -> Na a S + 4CO The sulphuric acid is

phate crystallised.

Calcium sulphate, CaS0 4

is

Fe +H 2 SO« - FeSO« + H a

loses its water of

Action of heat. On heating, iron(II) sulphate first
This salt occurs naturally as anhydrite, CaS0 and gypsum, being converted into a
4 ,
crystallisation, the original green crystals
CaS0 4 .2Ha O. For the use of anhydrite in making sulphuric acidand dirty-yellow anhydrous solid.
ammonium sulphate, see pp. 411 and 418.
Gypsum FeS0 4 .7H 2 -* FeS0 4 + 7H 2
is chiefly employed for the manufacture of plaster of
When more gives off sulphur dioxide (test—
strongly heated, it
Paris.
decolorisation of potassium permanganate solution) in addition to
Plaster ofParis (CaS0 4 )„.H 2 0, calcium sulphate hemihydrate. This
white fumes of sulphur trioxide, and leaves a
reddish-brown solid,
compound made by heating gypsum in large steel vessels of several
is
iron(III) oxide, 'jewellers' rouge'. This is used in pigments
Fe a O a
tons capacity. The gypsum is stirred mechanically and the tempera- ,

ture is maintained between 100°C and 200°C. (Venetian red, red ochre) and as a polishing powder.

2(CaS0 4 .2H 2 0)-v (CaSOJj.HjO

2FeS0 4 -»- Fe a a SO s SO„O + +
+ 3H 2
plaster of Paris Sulphuric acid was prepared by Glauber (1648) by distilling ironfll)
sulphate crystals. The sulphur trioxide given off in the second
stage
When mixed with water, plaster of Paris sets to a hard interlacing
mass of fine needles of gypsum, expanding at the same time. It is reacted with the water driven off in the first.

used for making casts for statuary (the expansion during setting H aO + S0 3 -»-H 2 S0 4
ensures a fine impression), in surgery to maintain joints in a fixed is used in the brown ring test for
nitrates (p. 436)
Iron(II) sulphate
position and in cements and wall-plasters. and it gives a similar colour with nitrogen monoxide (p. 448).
420 A NEW CERTIFICATE CHEMISTRY QUESTIONS 421

1000 parts of water), used in spraying vines and potatoes to

kill
Like all iron(TI) salts, iron(II) sulphate is a reducing agent, oper-
ating by electron loss, which converts iron(II) ions, Fe2+ , into moulds which would injure the plants. It is also used in the manu-
iron(lll) ions, Fe3+ For example, it reduces nitric acid to nitrogen
. facture of certain green pigments.
monoxide and chlorine to its ions. The two oxidising agents accept
the electrons lost by the iron(H) ions. Sulphites

The general properties of sulphites are discussed on p. 404.

6Fe*+ +
6H+ a+ 2HNO
-»- 6Fe 3+ 4H a 2NO + O+
2Fe8+ Cl ->- 2Fe 3+
+ a + 2CI- Ca(HSO a) a
Calcium hydrogen sulphite,
The iron(lI) sulphate is usually used in solution in dilute sulphuric
milk of lime (a
acid to prevent hydrolysis. This is prepared by passing sulphur dioxide into
of slaked lime and water) and is used for bleaching the pulp in
When exposed to air, iron(II) sulphate crystals become covered paste
paper-making.
with a brownish deposit of a basic iron(TII) sulphate, by a reaction
of the type: Ca(OH) a + 2SO -> Ca(HS0
a 3) a

12FeS0 4 + 6H O + 30,
t - 4{Fe 2 (S0 4)a .Fe(OH) s }
(from the air) QUESTIONS
Large quantities of iron(II) sulphate are used with gallic acid in
the manufacture of ink. This recipe has been known for more than 1. Give an account of the preparation and properties of hydrogen
2000 years. sulphide. . ......
hydrogen,
If a specimen of hydrogen sulphide were contaminated with
Ironflll) sulphate, Fe^SO^ how could you obtain the hydrogen sulphide free from hydrogen? (C.)
2. Starting from sulphur, describe how you
could prepare specimens of
This salt may
be prepared by oxidising iron(II) sulphate by nitric
plastic sulphur; (b) sulphur dioxide; (c) sulphur trioxide; and (d)
hydro-
(a)
acid in the presence of sulphuric acid (equation above).
gen sulphide. (N.U.J.B.)
It forms alums, for example K S0 .Fe (S0 how would you prepare:
2 4 a 1)3 .24H a O, which are 3. Starting with roll sulphur,
more important than iron(III) sulphate itself, because they can be (a) Rhombic crystals of sulphur?
more (b) Monoclinic (prismatic) crystals of
sulphur?
readily purified by crystallisation.
(c) Plastic sulphur? . .

Copper(II) sulphate (cupric sulphate), CuS0 4 Mention two other elements which, like sulphur, exist in more than one
variety. (C.)
'Blue vitriol', CuS0 4 .5H a O, is copper(II) sulphate pentahydrate.
4 Describe one laboratory method or preparing and collecting hydrogen
The preparation of the from copper is fully described on p. 231
salt
sulphide, and mention a suitable drying agent. What is the effect of passing
it may also be prepared from the oxide or carbonate of the metal and hydrogen sulphide into solutions of (a) copper sulphate; (6)
iron(III)

dilute sulphuric acid (p. 235). chloride; (r) chlorine; (d) ammonia; (e) litmus?
Briefly describe what happens when hydrogen sulphide
burns in (a) excess
On the large scale, it is made by first heating scrap copper with
of air; (b) a deficit of air. (B.)
sulphur,
Give an account of the important properties of hydrogen
sulphide.
5
Cu + S -> CuS A specimen of this gas prepared from iron(II) sulphide is found on analysis
that the iron(II)
and then oxidising the sulphide by heating it with access of air. to contain 10% by volume of free hydrogen. Assuming
calculate the
sulphide contained no other impurity than metallic iron,
CuS + 20 —> CuS0 4
a
percentage of free iron present. (L.)
6 From what sources is sulphur obtained? How can
The sulphate then crystallised.
is sulphur be used
When heated, the pentahydrate loses water of crystallisation and for the preparation of (a) sulphuric acid; (b)
sulphurous acid? (O and C.)
sulphide gas?
leaves white anydrous copper(II) sulphate (p. 208). 7 How would you prepare in the laboratory hydrogen
solution of lead
CuS0 4 .5H a O -> CuS0 4 Sketch the apparatus. What is the effect of the gas on (a) a
+ 5H O a
nitrate; (/>) sulphur dioxide; (c) bromine water?
(N.U.J.B.)
The formation of the blue pentahydrate from the anhydrous salt is
8. Give a short account of the chemical reactions which take place in
the
used as a test for water. manufacture of sulphuric acid.
Use. Copper(n) sulphate is used in making washes such as 'Bor- Describe experiments illustrating the action of this acid on metals. (U.
deaux mixture' (11 parts of lime and 16 parts of copper sulphate in and C.)
422 A NEW CERTIFICATE CHEMISTRY
9. Describe the properties of sulphuric acid.
Why is this compound regarded as (a) an acid;
(A) a dibasic acid? (O.
and C.)
10. How
would you prepare a quantity of dry sulphur dioxide? How
may be shosvn that the formula for this gas is SO,? (N.U.J.B.)
it

11. Describe briefly two distinct methods which could

preparation of sulphur dioxide.
be used for the Chapter 32
How is sulphur dioxide converted into sulphuric acid in the 'contact'
process?
What simple experiment shows that sulphur dioxide contains
its own
volume of oxygen? Nitrogen and Ammonia
12. Describe the preparation and collection of dry
sulphur dioxide in (For nitrogen in periodicity, see p. 84)
the laboratory. Mention, without giving details of the manufacturing
plants
how it is prepared on the industrial scale. What is the action of sulphur
dioxide on (a) water; (Z>) oxygen; (c) chlorine; (d) hydrogen
sulphide;
NITROGEN
(e) nitrogen dioxide? (B.)
Occurrence
1 3. Describe the preparation and collection of sulphur dioxide. Describe
an experiment to show that sulphur dioxide contains its own volume
of ABOUT four-fifths of the atmosphere free nitrogen. The element
is

oxygen. What additional information would you require in order to

deter- also occurs form of sodium
combined in the Chile nitrate, salt-
mine the molecular formula of sulphur dioxide? Show clearly how you petre, NaN0 3 , as a mineral deposit in Chile, and distributed every-
would use the results of the experiment, and the additional information
in where in the soil in minute quantities as ammonium sulphate
determining this formula. (N.U.J.B.)
14. Describe the reaction which takes place when copper is heated with
(NHJaSO^ and sodium nitrate, NaN0 3 potassium nitrate, KN03
, ,

concentrated sulphuric acid. The resulting gas is passed into (a) litmus and calcium nitrate Ca(N0 3 2 (The very great importance of these
) .

solution; (6) chlorine water; (c) a solution of hydrogen sulphide. What compounds of nitrogen in maintaining the fertility of the soil is dis-
would be observed in each case and what explanations would you give of cussed on p. 147.)
the results obtained? (L.)
Combined nitrogen is always found as a constituent of the living
15. Describe fully how to prepare and collect in the laboratory sulphur matter of plants and animals.
dioxide from sulphuric acid. How would you show the action of this gas
on (a) chlorine water; (6) moist hydrogen sulphide?
What takes place when a solution of the gas is allowed to stand in con- Preparation of nitrogen from the atmosphere
tact with air?
The gases present in dry air are oxygen, about 21% by volume,
Explain the above reactions by equations or otherwise. (N.U.J.B.)
carbon dioxide, about 0.03% by volume, and 'atmospheric nitrogen',
16. What is meant by the term allotropy? Describe the preparation of
two allotropic forms of sulphur. about 79% by volume. The first two of these gases can be removed
Starting from sulphur, how would you obtain fairly pure samples of and the nitrogen collected by the apparatus of Fig. 135.
(a) sulphur dioxide; (b) sulphur trioxide? (C.W.B.)
Copper to absorb
17. Describe, with a diagram, how you would prepare and collect Nitrogen
I Oxygen
hydrogen sulphide in the laboratory.
Describe how hydrogen sulphide reacts with (a) sulphur dioxide;
(Z>) iron(ril) chloride solution.
When electric sparks from an induction coil are passed for
some time
through a volume of hydrogen sulphide the gas is decomposed, sulphur is
deposited on the sides of the vessel and on cooling to the original con-
ditions hydrogen remains, the volume of which is equal to that of the
hydrogen sulphide. The vapour density of the hydrogen sulphide being 17
calculate from these facts the formula of hydrogen sulphide. (H, 1 ; S, 32.)
(N.U.J.B.)
\Caustic soda solution
to absorb Carbon Dioxide.
18. Explain the construction and the working of a Kipp's apparatus for
generating hydrogen sulphide. Describe and explain the effect of passing
Fig. 135.
the gas through aqueous solutions of (a) copper sulphate; (A) blue litmus; Preparation of nitrogen from tho air.
(c) chlorine. What happens if the resulting solution from (6) is boiled ? (L.)
423
 424 A NEW CERTIFICATE CHEMISTRY NITROGEN 425

The equations
Weigh out the two compounds in these proportions. 14 g of sodium
arc:

+ CO* g of ammonium chloride will be suitable

weights.
Absorption of carbon dioxide 2NaOH Na 2 C0 3 + H,0 nitrite and 1 1

Place the compounds in a round flask, add 350 cm of

3 water, fit up
Absorption of oxygen 2Cu + 2 2CuO
becomes
If the nitrogen is required dry, it may, after leaving the heated the apparatus as in Fig. 136 and heat gently. As the solution
warm, rapid effervescence occurs and the nitrogen evolved may be
copper, be passed through a U-tube containing glass beads wetted
with concentrated sulphuric acid to dry it and then collected over collected over water.
mercury. NH N0
4 2 (aq)
-»- N„(g) + 2H 2 0(1)

The product of this experiment is not pure nitrogen. It contains

Other chemical methods of preparation or nitrogen
about 1 %
by volume of the 'rare gases', chiefly argon, the removal of
which is not possible by chemical methods. The presence of these The action of chlorine on ammonia.
gases makes 'atmospheric nitrogen' denser than the pure gas. 3C1, + 8NH 3 -* N g + 6NH 4C1
Another method of preparing 'atmospheric' nitrogen is to absorb
both carbon dioxide and oxygen together by shaking air with a ammonia gas over heated copper(II) oxide (see p. 429).
Passing
solution of pyrogallol in sodium hydroxide solution. The sodium 2NH a + 3CuO-> 3Cu + N 2 + 3H 2
hydroxide absorbs the carbon dioxide and the pyrogallol absorbs Reduction of oxides of nitrogen by heated copper, e.g.,
the oxygen to form an oxidation product of itself.
2Cu(c) 2NO(g) -» 2CuO(c) + N,(g)
+
This method is, however, only suitable for the preparation of small heating of
These methods are all much less convenient than the
samples of 'atmospheric nitrogen'.
ammonium nitrite.

Preparation of nitrogen by heating ammonium nitrite

Tests for nitrogen
A solution of ammonium nitrite readily decomposes on slight
At ordinary temperatures, nitrogen is so inert that no positive
warming to give nitrogen. This decomposition occurs slowly' at
We can only show a given gas to be nitrogen by
tests can be applied.
ordinary temperatures, so that neither ammonium nitrite itself, nor
elimination of other possibilities.
gas-jar of the gas. It is
Solution of Lighted splint. Place a lighted splint into a
Sodium Nitrite and not burn. cannot, therefore, be any
extinguished and the gas does It
Ammonium Chloride
oxygen, dinitrogen oxide, or any
gas which supports combustion, e.g.,

combustible gas, e.g., hydrogen sulphide, carbon

monoxide, hydrogen
Nitrogen
gases such
Smelt. The gas has no smell. This distinguishes it from
ammonia, hydrochloric acid gas.
as sulphur dioxide,
gas with which
Action of lime-water. After the above tests the only
To distinguish it from
nitrogen may be confused is carbon dioxide.
Nitrogen leaves the lime-water un-
this, lime-water and shake.
add
changed; with carbon dioxide, the lime-water is turned milky.

Properties of nitrogen

Nitrogen is colourless and odourless. It is slightly lighter than

air
Fio. 136.
Preparation of nitrogen by a chemical method. soluble in water (about 2 volumes of the gas
and only slightly
dissolve in 100 volumes of water at ordinary temperature).
solution in water, should be kept in stock. The compound is pre-
Under ordinary conditions the gas is very inert, but, by applying
its

pared as required by a double decomposition reaction between made combine with

the results of much research, it has been to
sodium nitrite and ammonium chloride.
hydrogen to produce ammonia.
NaNO, + NH 4 C1 NaCl + NH N0 4 2 N 2 + 3H ^2NH 2 3
69 g 53.5 g ammonium Haber's Process, see p. 431.
nitrite For this reaction applied in
426 A NEW CERTIFICATE CHEMISTRY AMMONIA 427

Nitrogen will combine directly with many metals forming nitrides

e-g.,
ammonia
3Mg + N ->Mg N
g 3
magnesium
nitride
)1 \»
Card cover
To burn some magnesium ribbon in a crucible and
illustrate this,
allow the product to cool. Add a few drops of water
mixture. The choking smell is that of ammonia. It is
and smell the
calcium hydroxide
ammonium chloride
and
/
evolved by the
action of water on the magnesium nitride which was formed,
in small
amount, by combination of the magnesium with nitrogen
of the air.
Mg N, + 6H O
3 s ->-2NH 3 +3Mg(OH) 2
magnesium water ammonia magnesium quicklime to
nitride hydroxide dry the
ammonia
AMMONIA
This hydride of nitrogen, NH can be made in very small
3 ,
amounts
by heating nitrogenous organic materials such as hoofs and horns
of
animals. Its old name was, in fact, 'spirit of hartshorn'.

Preparation of ammonia
Ammonia may be prepared in the laboratory by heating any Fig. 137.
ammonium salt with an alkali. Usually a mixture of ammonium Preparation of ammonia gas.
chloride and calcium hydroxide (slaked lime, the cheapest alkali) is
used. Both are solids so they must be thoroughly ground first to give Ammonia is less dense than air and very soluble in water, so it is

a very fine mixture in which the reaction can occur satisfactorily. collected as shown by upward delivery.
Instead of calcium hydroxide, sodium hydroxide (or potassium
Ca(OH) i! + 2NH 4C1 -> CaCl + 2H 8 + a 2NH,(g) hydroxide) solution may be used, in which case the flask would be
74 g 2 x 53.5 g
107 g placed in the vertical position and heated on a tripod and gauze.

An excess of the slaked lime is preferable. Weigh out 25 NaOH + NH 4C1 -»- NH 8 + H,0 + NaCl
g of
slaked lime and 16 g of ammonium chloride. Grind the mixture well or OH- + NH 4 + -* NH 3 + H 2
in a mortar, place it in a round flask of resistance glass and set
up Ammonium sulphate may be used instead of ammonium chloride.
apparatus as in Fig. 137. The neck of the flask should slope towards
Ca(OH) a + (NH 4) s S0 4 -»- CaS0 4 + 2H 2 + 2NH 3
A as shown, because water will condense and, if allowed to run back 2NaOH + (NH 4) 8 S0 4 -* Na,S0 4 + 2H 2 + 2NH S
on to the hot flask, might break it. Heat the flask. Ammonia gas is
evolved. It is dried by a rather unusual drying agent, quicklime, CaO, To obtain ammonia gas in quantity

because it reacts with all the usual drying agents. Concentrated If several gas-jars are required, it is very convenient to
of ammonia
sulphuric acid is acidic and would absorb the gas, forming a salt, e.g., fill these by heating a concentrated solution of the gas in water. In
this case the flask containing the ammonium chloride and
slaked lime
2NH 3 + H 2 S0 4 -> (NHJ.SO, containing a
in the previous experiment is replaced by a vertical flask
while it reacts with calcium chloride, forming solid complex com- of ammonia. N.B. This is not, strictly speaking,
concentrated solution
pounds, e.g.,
a preparation of ammonia gas but merely obtaining the gas from its
CaCI 2 + 4NH 3 —> CaCI 2 .4NH 3 solution in water.
428 A NEW CERTIFICATE CHEMISTRY AMMONIA 429

Tests for ammonia 800 times their own volume of ammonia. This reduced the gas pres-
Smell. A characteristic choking smell. The choking smell sure inside the flask to only a fraction of its former value, atmospheric
is due to the fact that the gas temporarily paralyses the pressure. As soon as the clip A
was opened, the water was forced
respiratory muscles and breathing is checked. In large into the flask because the atmospheric pressure from outside over-
quantities, the gas causes asphyxiation. came the resistance of the reduced gas pressure inside the flask. The
Action with litmus. Expose damp red litmus paper to the water, entering as a fountain, dissolved the remaining ammonia,
gas. It is turned blue. Ammonia is the only common alkaline maintaining the fountain until only air was left in the flask. (A thin-
gas. walled flat-bottomed flask must not be used for this experiment; the
reduction of pressure inside would almost certainly cause it to collapse
Properties of ammonia inwards.)
Appearance. A colourless gas.
Action of ammonia with hydrogen chloride
Density. Lighter than air.
Place a gas-jar of ammonia over a gas-jar of hydrogen chloride,
Density relative to hydrogen, 8.5.
remove the covers and allow the gases to mix. Dense white fumes will
Density of air relative to hydrogen,
be seen which will settle to a white solid, sal-ammoniac or ammonium
14.4.

chloride, on the sides of the gas-jar.

Solubility of ammonia in water. The fountain experiment
NH 3 (g) + HCl(g)-*NH 4 CI(c)
The very great solubility of ammonia in water is illustrated in the
fountain experiment (Fig. 138). Replace the gas-jar of Fig. 137 by a Ammonia as a reducing agent
dry, thick-walled flask of about 1500 cm 3 capacity and pass ammonia Action of ammonia on chlorine. This is fully considered on p. 1 14.
some apparatus
into it for time. (It is better Action of ammonia on heated copper(ll) oxide. Set up the
to supply another flask with fresh as shown in Fig. 139. The colourless liquid collecting at
is water A
reaction mixture, to give off a satis-
factory stream of ammonia.) Fit Granular copper ( II ) oxide nitrogen
the flask with a rubber stopper Dry
carrying tubes and clips as shown. ammonia -f
Place the tubes and clips under
water, open clip B for a moment, Gas Furnace
close it and allow the few drops of
water which have entered to run
down into the round part of the
flask. Then replace the tubes and
water water
clips under water and open clip A.
Fio. 139.
A fountain will at once play, as in oxide.
Fio. 138. Action of ammonia on copperflO
sketch, and continue until the
will
Fountain experiment. flask is as full of water as it was at B is nitrogen (for tests
(for tests, see p. 270) and the colourless gas
formerly full of ammonia. copper(II) oxide to copper
see p. 425). The ammonia has reduced the
The alkaline nature of ammonia can be shown in this experiment nitrogen and water.
by adding a and has itself been oxidised to
litmus solution to the water in the trough and
little

making it turn red by the addition of a drop of acid. When the 3CuO(c) -I- 2NH 3 (g) -> 3Cu(c) + 3H gO + N 2 (g)
Combustion of ammonia. Ammonia will burn in an atmosphere
ammonia dissolves in the litmus solution, the latter is turned blue. of
Explanation. Ammonia has the highest solubility of all known gases slightly enriched by oxygen but not in air alone. The chief pro-
air
(about 800 vol. of gas in 1 vol. of water at 15°C). The first few drops ducts are nitrogen and water.
of water, which entered when clip B was opened, dissolved nearly 4NH 3 + 30 s -> 2N + 6H 2Q 2
430 A NEW CERTIFICATE CHEMISTRY AMMONIA 431

Liquefaction of ammonia gas It will also neutralise acids forming ammonium salts, which can be
Ammonia gas can be liquefied at ordinary temperatures by com- crystallised out and are generally similar to ordinary metallic salts, e.g.,
pression. The colourless liquid boils at about 33°C under ordinary — NaOH + HCl-J-NaCl + HjO \
atmospheric pressures. NH 4OH + HC1 -»- NH C1 + H,0/ 4
Formula of ammonia gas — see p. 1 14 and p. 74.
2NaOH + H S0 4 -* Na S0 4 + 2H aO \
2 2

Ammonium hydroxide, NH OH
4
2NH 4OH + H 2S0 4 -> (NH«) S0 + 2H Oj a 4 2

Set up apparatus as in Fig. 140, and heat the flask gently as in the Notice that ammonium salts, though often written in molecular form,
preparation of ammonia gas. The rim of the inverted funnel should are actually electrovalent compounds, containing the ammonium ion,
just touch the surface of the water. This is a device to prevent the NH + , in combination with a corresponding amount of an acidic
4

water from 'sucking back' into the flask. After a time the water in ion,such as CI" or
_
NO
a . Since the
ammonia molecule S can NH
the beaker will be found to have acquired the smell of ammonia gas combine with a hydrogen ion (proton), it must be regarded as a base.

which has dissolved in it. The solution is known as ammonium hydrox- NH 3 + H + ^NH 4 + (Seep. 70)
ide. At 0°C and ordinary pressure, one volume of water dissolves It is a much weaker base than the hydroxide ion so ammonium salts

of strong acids are considerably hydrolysed in their aqueous solu-

ammonium chloride and tions and these solutions show appreciable acidity.
calcium hydroxide
Uses of ammonia
(1) solution is used in laundry work. It removes tem-
Ammonia
porary hardness by precipitating the calcium ion of calcium hydrogen
carbonate as chalk.
»-
Ca»+ + 2HCO„- + 20H- -*- CaCO s + 2H 2 + C0 3

It also dissolves out acids left by evaporation of perspiration from

water underclothing.
Ammonia is converted to nitric acid. (See p. 452.)
(2)
(3) Ammonium sulphate is
made from ammonia to be used as a
nitrogenous fertiliser. This may be done by direct neutralisation with
sulphuric acid or by passing carbon dioxide and ammonia through a
Fig. 140. steam-heated mixture of calcium sulphate (anhydrite) and water.
Preparation of ammonium hydroxide solution. CaS0 4 + 2NH 3 + CO + H a 2
-* CaC0 3 + (NHJgSO,
Chalk is filtered off and ammonium sulphate can be crystallised.
about 1000 volumes of the gas. Some of this gas combines chemically ammonia used in refrigerating plant.
(4) Liquid is
with the water to form ammonium hydroxide, which
acts as a weak
base, ionising slightly (about 0.4% in normal solution), as: Manufacture of ammonia. Haber's process
NH + H
3 2 v± NH 4
+ + OH- This process affords a good example of the effects of various
The hydroxyl factors (e.g., temperature, pressure, concentration) on chemical re-
ion, OH-, gives the solution its alkaline reaction to-
wards litmus and many properties resembling those action and the way in which industrial practice is influenced. The
of the caustic
alkalis, Na + OH- and K+OH". Like general situation is summarised in Le Chatelier's Principle, which
them, it will precipitate in-
soluble metallic hydroxides when mixed with solutions states:
of salts or the
of the
metals, e.g., If a chemical system is in equilibrium and one
factors involved in the equilibrium is altered,
the equi-
3K.OH + FeCls -> Fe(OH) 3 1 + 3KC1 librium will shift so as to tend to annul the effect of the
3NH 4 OH + FeCl 3 -»- Fe(OH) 3 ,
+ 3NH C1 4 change.
T 432 A NEW CERTIFICATE CHEMISTRY
Haber's process uses the reaction:
AMMONIA
from Durham, and limestone from the Tees and Wear
433

valleys.
coal
N,(g) + 3H 2 (g) 2NH 3 (g) There is also easy transport by sea for fertilisers to Europe.
1 vol. 3 vol. 2 vol. at constant T. and P.
Action of alkalis on ammonium salts
The reaction (from left to right) is exothermic, i.e., liberates heat.
Effect of pressure. Ammonia is produced from itselements with Any ammonium salt, if heated with sodium hydroxide (or po-
reduction of volume. Therefore, if the system is in equilibrium and tassium hydroxide) solution or with calcium hydroxide and a little
the pressure is then raised, the equilibrium must shift so as to tend to water, gives off ammonia gas (which turns red litmus paper blue).
lower the pressure (Le Chatelier's Principle). To do this, the volume This distinguishes ammonium salts from those of any metal.
must be reduced by production of more ammonia. That is, high NH« + + OH- ->- NH + H aO 3
pressure favours production of ammonia.
Effect of temperature. The formation of ammonia from its elements Action of heat on ammonium salts

is an exothermic change. If the system is in equilibrium and the Sublimation. Ammonium salts are always decomposed by heat
temperature is then lowered, the equilibrium must shift so as to tend and, sometimes, sublime. The best example of sublimation is provided
to raise the temperature again (Le Chatelier's Principle). That is, heat by ammonium chloride.
must be liberated by the production of more ammonia. That is, low Place a little ammonium chloride in a dry test-tube and heat gently.
temperature favours the production of ammonia. But lowering of The effects shown in Fig. 141 will be observed.
temperature reduces the rate of reaction, so it is necessary to introduce
a catalyst which will give a sufficient reaction rate in spite of a rela-
tively low temperature.
Effect of concentration. If the system is in equilibrium and more
nitrogen is then added to increase its concentration, Le Chatelier's

Principle requires the equilibrium to shift so as to tend to reduce the

nitrogen concentration. That is, more ammonia will be produced to White
Sublimate of
use up nitrogen. This increases the yield of ammonia relative to Ammonium
hydrogen, and vice versa if the hydrogen concentration is increased. Chloride
However, in practice, there is no particular advantage in using excess So/id
of either material; the gases are used in the theoretical proportion of Ammonium
Chloride
nitrogen to hydrogen, 1 3 by volume.
:

The conditions chosen in accordance with the above discussion

are:
very high pressure (200-500 atm) Fig. 141.
temperature about 450°C. Action of heat on ammonium chloride.

catalyst: finely divided reduced iron, usually

'promoted' by alumina. Usually when a vapour is cooled, it condenses first to a liquid, and,

Hydrogen is manufactured from hydrocarbons and nitrogen from the later,on further cooling, solidifies, e.g., steam -> water -* ice.
air. They are mixed in the required 3 1 proportion by volume and
:
The characteristic feature of sublimation is that, on cooling, the

vapour condenses directly to the solid without the intermediate

dried (e.g., by silica gel). They are pre-heated by gases leaving the
catalyst chamber and are then passed over the catalyst at 450°C. The liquid state. Usually, the converse is also true, that the subliming
solid is converted directly to vapour on heating without an
inter-
ammonia produced is absorbed in water or liquefied by refrigeration
mediate liquid stage, but in some cases (for example, that of iodine)
and the unused gases are recirculated.
melting may occur.
N t + 3H 2 -»-2NH3 Very few substances sublime. Among those which sublime are a
The ammonia and sulphuric acid industries on the Tees have the ammonium salts (especially the chloride), iodine and naphtha-
few
advantage of immediately adjacent deposits of anhydrite (CaSO^), of means of purifying them, because
lene. Sublimation is a very effective
434 A NEW CERTIFICATE CHEMISTRY
their impurities are very unlikely to sublime. The white sublimate of
ammonium chloride in Fig. 141 will be a purer sample of the com-
pound than the original material used for the experiment. For
thermal dissociation, see p. 159.
Decomposition of ammonium salts by heat. Ammonium salts of
Chapter 33
acids having a high proportion of oxygen are usually decomposed by
heat, e.g.

(i) Ammonium nitrite. Nitric Acid and the Nitrates

NH NO s ^-N 2 + 2H O
4 t

This reaction is fully dealt with on p. 424.

(ii) Ammonium nitrate.
NITRIC ACID
NH 4 N08 -»-N,0 + old name for nitric acid was 'aqua fortis'— strong water. It

dinitrogen
2H ! THE
was so because
called it attacks so many substances, including
oxide
almost all the metals.
This reaction is fully considered on p. 445.
Preparation of nitric acid
the apparatus of Fig. 142. Into the
bulb of the retort put
Set up
concentrated sulphuric acid.
Questions on this chapter will be found on page 453. some potassium nitrate crystals and add

Fio. 142.
Preparation of nitric acid.

The potassium nitrate gradually dissolves and

Heat the retort gently.
effervescence occurs.
KNO a + H S0 a 4
K.HSO4 + HNO s
potassium
hydrogen
sulphate
435
 NITRIC ACID 437
436 A NEW CERTIFICATE CHEMISTRY
The nitric acid distils and a yellow
collects in the cooled receiver as Properties of nitric acid
liquid, while drops of the acid can be seen running down the bulb and Nitric acid a colourless, fuming liquid of density 1.5 g/cm* and
is

neck of the retort. The brown fumes are nitrogen dioxide formed by boiling point 85°C at ordinary atmospheric pressure. The ordinary
slight decomposition of the nitric acid by heat, concentrated nitric acid, as sold, contains about 70% by weight of the
4HN0 3 -» 2H 2 + 4NO, + O, pure acid and 30% of water. The pure acid is corrosive and destroys
nitrogen organic matter very readily. The skin is stained yellow by it and, if the
dioxide acid is left in contact with it for even a very short time, the skin is
and they impart a yellow colour to the acid by dissolving in it. destroyed.
This reaction is a general one. Any metallic nitrate, when heated
with concentrated sulphuric acid, gives off nitric acid, e.g., Chemical properties of nitric acid. Nitric acid can behave
chemically in two ways:
NaN0 3 + H,SO« -> NaHS0 4 + HNO s
sodium nitrate It is (1) a very strong acid,
Pb(NO s) g + H,S0 4 -> PbSO« + 2HNO s (2) a powerful oxidising agent.
lead(ll) nitrate

Nitric acid acting as an acid

Manufacture
Nitric acid is a very strong acid, being almost completely ionised in
Some manufactured by the above laboratory process.
nitric acid is
dilute solution with the production of hydrogen ion and the
nitrate
Iron retorts are used, because this metal is only slightly attacked by _
the acid, which is condensed in silica condensers. The nitrate em- ion, N0 3 .
~
ployed is sodium nitrate, NaN0 3 'Chile saltpetre* (see p. 442). An-
,
HNO ^ H + + N0
s 3

modified to
other method of manufacture is oxidation of ammonia (p. 452). This ionisation confers on it the usual acidic properties,
Nitric acid is used mainly for the manufacture of explosives and dyes. some extent by the powerful oxidising action of the acid.
(a) Nitric acid neutralises bases, forming metallic
nitrates, e.g.,
Test for soluble nitrates
K+OH- + H + N0 4 - -* K + NO s - + H 2
Crush a few potassium nitrate crystals in a mortar and put them
Cu 2+ O z - + 2(H + N0 3 -) -* Cu* (NO,-), + H 8
+
into a test-tube and add water to a depth of about 2 cm. Shake to
dissolve the potassium nitrate. Add a little dilute sulphuric acid and A account of reactions of this type is given in Chapter 16, pp.
full

then two or three crystals of iron(II) sulphate, which have also been 222-37.
(b) Nitric acid liberates carbon dioxide in reaction
with metallic
crushed. Shake to dissolve them. Hold the test-tube in a slanting
position and pour a slow continuous stream of concentrated sul- carbonate, as:
phuric acid down the side. (Care!) It will form a separate layer under- C0 3
*" + 2H + -»- H 2 + CO,
neath the aqueous layer and, at the junction of the two, a brown ring remember that all metallic nitrates are soluble in water.
It is useful to
will be seen. This brown ring is the characteristic test for a soluble when dilute, they react
(c) It is characteristic of strong acids that,
nitrate.
with the more electropositive metals, liberating hydrogen, as:
Explanation. The concentrated sulphuric acid and the nitrate yield
nitric acid.
(or Mg) 2H + -»- Zns+ (or Mg J+ ) H,
Zn + +
KNO s -f H 2S0 4
-»- KHS0 4 + HNO s This reaction cannot occur in this simple form with nitric acid;
it is

The nitric acid is then reduced by some of the iron(II) sulphate to complicated by the fact that nitric acid is a powerful oxidising agent.

nitrogen monoxide, NO. Any hydrogen initially produced by the action of a metal on nitric
6FeSO« + 2HNO-, + 3H,SO« - 3Fe 2 (S0 4) 3 + 4H + 2NO acid is at once oxidised by more of the acid to
water, and the reduc-

tion products of the acid are liberated. These may include

2 nitrogen
iron(lll) sulphate
even ammonia, which at once con-
The nitric oxide reacts with more ironfjl) sulphate to give the brown dioxide, nitrogen monoxide or is

compound FeS0 4 .NO, which appears as verted, by excess of the acid, to ammonium nitrate. Exact equations
the brown ring.
cannot be written because the reactions are always complex. If,
FeS0 4 + NO ->- FeS0 4 .NO
438 A NEW CERTIFICATE CHEMISTRY NITRIC ACID 439

however, copper is used with the concentrated acid, the principal S + 4H,0 -v H s S0 4 -f 6H + -I- 6e~
reaction is:
The electrons arc accepted by the acid in its capacity of oxidising
Cu + 4HNO, -»• Cu(N0 3 + 2H )2 2 + 2NO, agent.
If the concentrated acid is diluted with its own volume of water, 6HN0 3 +- 6H + + 6e~ -»- 6H O 4- 6NO, t
copper gives the principal reaction: given by adding these two electronic
The molecular equation above is
3Cu + 8HN0 3 ->- 3Cu(N03), + 4H O + 2NO s equations.
This is the usual laboratory preparation of nitrogen monoxide. The
important point is that, if nitric acid acts with a metal under ordinary ex- The oxidising action of nitric acid on an iron(II) salt
perimental conditions, the product is never hydrogen; it is a reduction Dissolve a few crystals of iron(II) sulphate in dilute sulphuric acid
product of the acid, such as nitrogen dioxide, nitrogen monoxide in a test-tube. Add a little concentrated nitric acid and heat. 1 Brown
or ammonium nitrate. If, however, very dilute nitric acid is used fumes of nitrogen dioxide are seen and a brown or yellow solution
(about 1%) with magnesium or manganese, some hydrogen will be is left, instead of the original pale green solution.
produced, escaping oxidation because of the very dilute condition of The nitric acid has oxidised the green iron(II) sulphate to brown
the acid. The hydrogen is not pure, being accompanied to some or yellow iron(III) sulphate and has itself been reduced to nitrogen
extent by reduction products of the acid. monoxide which, in the air, forms nitrogen dioxide (p. 448).

Nitric acid as an oxidising agent 6FeS0 4 + 3H.S0 4 + 2HN0 3 -> 3Fe 2(SO«) 3 + 4H 2 + 2NO
Like oxidising agents an acceptor of
2NO + 2 -v 2NO s
in general, nitric acid acts as
of the
electrons. It can do this in several different ways. Two of the more air
important ones are:
An important point to notice about nitric acid as an
4HN0 3 + 2e~ -* 2NO a " + 2H a O + 2NO a oxidiser is that introduces no solid into a mixture. The
it

8HNO3 + 6e- -> 6NO3- + 4H aO + 2NO acid itself is volatile and its reduction products, oxides of
giving nitrogen dioxide and nitrogen monoxide. The electrons are nitrogen, are gaseous, while the other product, water, can
supplied by the reducing agent which takes part in the reaction. This also be evaporated off. Thus, it leaves no solids to compli-
is often a metal, e.g., copper. This forms ions, as: Cu » Cu 2+ 2e~. — + cate purification of the product of oxidation.
By combining this ionisation with the two equations given above, the
Other oxidising actions of hot, concentrated nitric acid are:
reactions shown between copper and nitric acid in the last paragraph
Carbon to carbon dioxide.
are obtained. Other metals give similar behaviour, varying in detail
with the nature of the metal, the concentration of the acid and the C + 4HN0 3
->- 2H 2 + 4NO, + CO,
temperature employed. Red phosphorus to orthophosphoric acid.
Nitric acid also oxidises certain non-metallic elements and certain P + 5HN0 3 -> H 3 P0 4 + 5N0 2 + H tO
compounds; examples are given in the following paragraphs. orthophosphoric
acid
The oxidising action of nitric acid on sulphur

If concentrated nitric acid (which contains 70% HN0 3 and 30% The action of heat on concentrated nitric acid
water), is warmed with powdered sulphur, brown fumes of nitrogen A clay pipe is used for this experiment because a fairly high
dioxide are evolved and sulphuric acid is left in solution. Bromine temperature is needed and the liquid nitric acid would break a heated
catalyses this reaction. glass tube. Fit up apparatus as in Fig. 143, omitting, for the present,
S + 6HN0 3 ->- H 2 SO« + 2H 2 + 6NO, the boiling-tube, and raising the end of the pipe stem above the water
level.
In electronic terms, the presence of the powerful oxidising agent, hot
concentrated nitric acid, enables the sulphur-water system to make 1 Before heating, the solution will be very dark brown or black. For an ex-

electrons available and so act as a reducing agent. planation of this, sec the 'brown ring' test (p. 436).
440 A NEW CERTIFICATE CHEMISTRY NITRATES 441

Concentrated
Al(OH) 3 3HN0 3 -* Al(NO s ) 3 + 3H,0
Oxygen
Nitric acid It shows the usual behaviour of the nitrate of a heavy metal when
heated.
4A1(N0 3) 3 -+ 2A1,0, + 12NO, + 30»

Ammonium nitrate, N ..\0 1 1

:;

This compound may be made in the laboratory by neutralisation

of ammonium hydroxide by nitric acid (p. 233).
Fig. 143. NH OH + HNO
4 a
-»- NH,N0 3 |- HO a
Decomposition of nitric acid by heat.
It is and very soluble in water. When it dissolves, heat is
colourless
Heat the pipe stem to red heat at one point with a Bunsen burner absorbed and, by dissolving a large quantity of the salt in water, a
and pour concentrated nitric acid into the bowl of the pipe. Clouds liquid of low temperature is rapidly obtained and may be used as a
of brown fumes emerging from the pipe stem show that nitrogen 'freezing-mixture'.
dioxide produced.
is Ammonium nitrate is decomposed by heat into dinitrogen oxide

Now, complete the apparatus as in Fig. 143, making sure that the and water (p. 445).

end of the pipe stem is the least possible distance below the water-level NH N0 3 -> N O + 2H,0
4 t
and starting with the boiling-tube full of water. As the nitric acid experiment is carried out in a test-tube, the usual test for
If the
runs over the red-hot pipe stem, a colourless gas collects in the boiling-
dinitrogen oxide (rekindling of a glowing splint) will be masked by
tube. Test it with a glowing splint. It is rekindled. The gas is oxygen.
the steam which is also given off. If the heating is carried on to de-
(Nitrogen dioxide, also produced as above, is soluble in water.)
compose all the ammonium nitrate, there will be no residue and the
The third product of the decomposition of the acid is water. last traces of the salt will decompose with explosion.
4HN0 3 -»• 2H 2 + 4NO, + O, A mixture of ammonium nitrate and aluminium powder is used as
an explosive, 'ammonal'. When it is detonated, the following re-
NITRATES action occurs.

K Nitrates of these metals are decomposed by 2A1 + 3NH<N0 3 -*- A1,0 + 3N + 6H,0 3 8

Na heat to the nitrite and oxygen. The gaseous nitrogen and steam, having a volume many times greater

Ca All than that of the original solids, produce a very high pressure and
Mg Nitrates of these metals are decomposed on nitrates hence an explosion.
Al heating to the oxide of the metal, nitrogen are
soluble
Potassium nitrate (nitre, saltpetre), KNO a
Zn dioxide and oxygen.
Fe in In the laboratory, this salt may be obtained by neutralisation

Pb water. (p. 233).

Cu KOH !- HN0 3 ->* KNO + H O s t

Nitrates of these metals are decomposed on On the industrial scale,prepared by double decomposition
it is
Hg heating to the metal, nitrogen dioxide and between potassium chloride (from the Stassfurt deposits) and sodium
Ag oxygen. nitrate (from Chile).

Aluminium nitrate, A1(N0 3 ) 3 .9H 2 KC1 + NaN0 -* KN0 + NaCl

3 3

This isan unimportant salt. It can be prepared by dissolving Boiling saturated solutions of potassium chloride and sodium nitrate
freshly prepared aluminium hydroxide in dilute nitric acid and are used and sodium chloride, being the least soluble of the four salts
crystallising in the usual way. at this temperature, crystallises and is filtered off. On cooling to
442 A NEW CERTIFICATE CHEMISTRY NITRATES 443
ordinary temperature, potassium nitrate crystallises as it is the least Calcium nitrate, Ca(NO s) a
soluble of the four salts at this temperature.
This compound may be made in the laboratory by the action of
When heated, potassium nitrate melts to a colourless liquid and
nitric acid upon slaked lime or chalk.
decomposes slowly, liberating oxygen (test: glowing splint rekindled)
and leaving, when cool, a pale yellow solid, potassium nitrite. Ca(OH) a + 2HN0 3 + 2H aO
Ca(N0 3) a
2KN0 3 - 2KNO a +O a
CaC0 3 + 2HN0 3 CaiW)^ + H aO + CO,
Potassium nitrate is chiefly used for the making of fireworks and It is usually met with as the tetrahydrate, Ca(N0 3 ) 3 .4H a O, which
gunpowder, which usually contains about one part of charcoal, one forms white deliquescent crystals.
part of sulphur and six parts of potassium nitrate (by weight). When In industry, some calcium nitrate (mixed with lime) is used as a
ignited, the mixture burns rapidly, producing nitrogen, oxides of fertiliser, 'air saltpetre'. It is prepared from the nitric
acid obtained
carbon and sulphur and other gases. These hot gases occupy a much by oxidising ammonia.
greater volume than the original solids, and a very great pressure is For the action of heat on calcium nitrate, see below.
set up which is used for propulsion or disruption.

Sodium nitrate (Chile saltpetre), NaN0 3 Nitrates of magnesium, zinc, lead, copper
These compounds are prepared, as explained in Chapter 16, by
all
Large deposits of sodium mixed with clay, occur in Chile,
nitrate,
the action of nitric acid on the metal or on its oxide, hydroxide or
as 'caliche'. The material is broken up by blasting. The sodium
carbonate. Except leadfll) nitrate, which crystallises anhydrous,
nitrate is extracted by dissolving it out in water and evaporating the
they form hydrated crystals. All the crystals are white in colour
solutions by the heat of the sun. The area where the nitrates are all

found is practically rainless and water is supplied for the process by except those of copper(II) nitrate, which are blue.
pipe-lines. The most important property of these nitrates is the reaction they
example lead
In the laboratory, sodium nitrate may be prepared by neutralising undergo when heated. This is as follows (taking for
causticsoda with nitric acid (p. 233).
Place a little lead(ll) nitrate in a test-tube and
heat it. series of A
NaOH + HN0 3 -> NaN0 3 + H a O almost small explosions, is heard. (This effect
sharp cracking sounds,
When heated, sodium nitrate behaves exactly like potassium is called decrepitation.) Later, the lead(II) nitrate melts and effer-
with
nitrate (see last section).
vesces, giving off brown fumes (nitrogen dioxide). Test the gas
2NaN0 3 ->- 2NaNO a + a glowing splint. The Hence oxygen is also present
splint is rekindled.
3
The solid residue is reddish brown when hot and yellow when cold.
The most important use of sodium nitrate is its application to the
oxide), and will probably be found to be fused
land as a fertiliser (see p. 452). It is rapid in action and is applied in It is litharge (lead(ll)

spring. into the glass.

The Chilean deposits used to be the only source of nitrogenous 2Pb(NO a) a -> 2PbO + 4NO + O
a a
'chemical' fertiliser, but the Haber process (p. 431) now furnishes
heat on the nitrates of com-
alternative supplies. This reaction is typical of the action of
(Note that also exactly analogous to the
Large quantities of sodium nitrate are also used for the manu- mon heavy metals. it is

facture of nitric acid (p. 436), potassium nitrate (see p. 441), and action of heat on nitric acid, p. 436).
nitrates of
sodium nitrite. This substance is used extensively in the manu- The following equations express the reaction for other
cases, the experimental observations are exactly
facture of aniline dyes, and is made by heating sodium nitrate with heavy metals. In all
the oxides, which are stated. With
carbon or lead. The presence of these reducing agents hastens the as above except for the colours of
the nitrates given below there is no
decrepitation.
conversion of the nitrate to the nitrite, a process which is slow if heat
alone is employed. 2Ca(N0 3) a . 2CaO + 4NO + O
a a

NaNOa + Pb-> NaNO a + PbO white calcium

2NaN0 3 + C -
2NaN0 2 + CO a
oxide
(white)
444 ANEW CERTIFICATE CHEMISTRY
2Mg(N0 3) 2 -+ 2MgO + 4NO s + O,
white magnesium
oxide
(white)

2Zn(N0 3 ) 2 -»- 2ZnO + 4NO g + O,

white zinc oxide
(yellow when hot; Chapter 34
white when cold)

2Cu(NOa) a -*- 2CuO + 4N0 + O,

4
green copper(II) oxide
(black)
Oxides of Nitrogen
Mercury(II) and silver nitrates
The oxides of mercury and silver are decomposed by heat, there-
two metals leave the free metals when heated.
fore the nitrates of these DINITROGEN OXIDE
2AgN0 3 > 2Ag + 2NO g + O, (formerly called nitrous oxide)
silver
compound is most conveniently prepared by the action of
Hg(NO a ) 2 * Hg + 2NO. 4- O t
THIS
mercury heat on ammonium nitrate (Fig. 144).

ammonium
Questions on this chapter will be found on page 453.
nitrate

Fio. 144.
Preparation of dinitrogcn oxide.

On heating, the ammonium nitrate melts and effervesces. Di-

nitrogen oxide and steam are given off. Most of the steam is con-
densed to water as the bubbles pass up the gas-jar.
NH 4N0 3 -»-N 2 + 2H 8

Ammonium nitrate will explode, if the amount of

on heating,
material in the vessel becomes very small, but the reaction is quite
safe unless this happens. If desired, the gas may be prepared by
heat-

ing any mixture of salts which, by double decomposition, will yield

ammonium nitrate— e.g., a mixture of potassium nitrate and am-
monium sulphate, finely ground.
445
446 NEW CERTIFICATE CHEMISTRY
A NITROGEN MONOXIDE 447

(NHJ^SO, + 2K.NO3 -*- 2NH 4 N0 3 + K,S0 4 Combustion of a candle, sulphur, carbon, and phosphorus
This mixture is less liable to explode. These materials are placed on deflagrating spoons and made to
Test for dinilrogen oxide
burn by heating in a Bunsen flame. (The candle is, of course, merely
lighted.) When plunged into dinitrogen oxide, they all burn more
The gas rekindles a brightly glowing splint.
vigorously than in air, the candle with its familiar yellow flame,
It may be distinguished from oxygen by the following
sulphur with a blue flame, and phosphorus with a bright yellow
tests:
flame. The oxides of the burning elements are formed and gaseous
Dinitrogen oxide has a sweet and sickly smell (oxygen has
nitrogen.
no smell). "
+ 2N,0 -» CO, + 2N,
Invert a gas-jar of dinitrogen oxide over cold water and
shake it. The level of water in the gas-jar will rise, showing
the gas to be fairly soluble in water. Oxygen is almost
candle wax
£ + N,0 -* H,0 + N,
C + 2N,0 ->• CO, + 2N,
carbon
insoluble in water and no rise would be observed. dioxide
Dinitrogen oxide does not give brown fumes with nitrogen S + 2N,0 -> SO, + 2N,
monoxide. If a little oxygen is bubbled up into a volume of sulphur
nitrogen monoxide enclosed over water, brown fumes of dioxide

nitrogen dioxide are formed. 4P + lONgO -> P«O 10 + ION,

dense white
Properties of dinitrogen oxide fumes;
phosphorus
The gas is and has a rather sweet,
colourless, neutral to litmus pentoxide
sickly smell. It can produce insensibility for short periods and is used Feebly burning sulphur may be extinguished by dinitrogen oxide.
as an anaesthetic for minor surgical operations, such as are required For the explanation of this, see the action of dinitrogen oxide on a
in dentistry. Insensibility lasts for a minute or two only. The period
glowing splint (above).
of insensibility can be prolonged if the gas is mixed with about 20%
oxygen and inhaled, the oxygen being necessary to keep the patient Formula of dinitrogen oxide
alive. A trace of carbon dioxide must also be present to stimulate the
See p. 118.
respiratory centres and maintain breathing. Patients recovering from
the effects of dinitrogen oxide may become hysterical; hence its com-
mon name — 'laughing gas'.
NITROGEN MONOXIDE
Density. Dinitrogen oxide has a density of 22 compared with
hydrogen. (Molecular weight of dinitrogen oxide = 44.) (formerly called nitric oxide)
Solubility. The gas is fairly soluble in cold water. produced, mixed always with other oxides
Nitrogen monoxide is

of nitrogen, by the action of nitric acid on most metals.

The common-
Dinitrogen oxide as a supporter of combustion
used that of moderately concentrated nitric acid on
est reaction is
Action on a glowing splint. If the splint is glowing brightly, copper
copper. Set up the apparatus shown in Fig. 145. Cover the
it will
be rekindled by dinitrogen oxide, but, if only feebly glowing, it will nitric acid, about equal in volume
with water and add concentrated
be extinguished.
to the water. Vigorous effervescence occurs and the
flask is filled
To be rekindled, the glowing portion of the splint must be hot
brown fumes. These are nitrogen dioxide produced partly by
with
enough to decompose some dinitrogen oxide into nitrogen and by oxidation of
the action of the acid upon the copper and partly the
oxygen. The mixture will then be rich enough in oxygen to stimulate by the oxygen of the air in the flask.
the main product, nitric oxide,
the combustion of the splint and cause it to burst into flame. A
feebly glowing splint will not be hot enough to decompose the
2NO + O, -»- 2NO,
nitrogen
dinitrogen oxide, and so will be extinguished, having no free oxygen dioxide
with which to burn.
The brown fumes dissolve in the water over which the nitrogen
448 A NEW CERTIFICATE CHEMISTRY NITROGEN DIOXIDE 449

Cone, nitric acid and water Nitrogen monoxide as a supporter of combustion

{equal volumes)
Nitrogen monoxide will support the combustion of those burning
materials whose flames are hot enough to decompose it and so
liberate free oxygen with which the material may combine. A splint,
nitrogen
candle, sulphur and glowing charcoal are all extinguished by the gas,
monoxide
but it supports the combustion of strongly burning phosphorus or
magnesium.

2Mg + 2NO -» 2MgO + N,

copper Formula of nitrogen monoxide.
Seep. 117.
Fig. 145.
Preparation of nitrogen monoxide.

NITROGEN DIOXIDE, NO a or N,0 4

monoxide is collected as a colourless gas. A green solution of Preparation
copper(II) nitrate is left in the flask. when
Nitrogen dioxide is given off, together with oxygen, nitrates
3Cu + 8HNO -» 3Cu(N0 3 + 4H O + 2NO
s )a a of heavy metals are heated. The most suitable nitrate to use is leadfjl)
Tests for nitrogen monoxide nitrate, because it crystallises without water of crystallisation, which
Exposure to air. Remove the cover from a gas-jar of is found in crystals of most nitrates and which
would interfere with
nitrogen monoxide. Reddish-brown fumes are at once pro- the preparation.
duced by oxidation of the gas by oxygen of the air. The lead(TT) nitrate decrepitates and melts on heating. It effervesces.

2NO + 0,-»-2N0 2
Nitrogen monoxide is the only gas to give this action. lead (E)
Action on iron(II) sulphate solution. Prepare a cold solu- nitrate
tion of iron(II) sulphate in dilute sulphuric acid. Pour it into
a gas-jar of nitrogen monoxide. The dark brown or black
Ice-salt
coloration is caused by formation of a black compound,
(FeSOJ.NO.
nitrogen
FeS0 4 + NO -> (FeS0 4 ).NO
dioxide
(The gas can be obtained in a pure state by heating this
compound.)
Fio. 146.
Preparation of nitrogen dioxide.
Properties of nitrogen monoxide
Nitrogen monoxide is colourless and almost insoluble in water. Its giving a gas, nitrogen dioxide, and oxygen. The nitrogen
brown
density is 15 times that of hydrogen; it is slightly denser than air of dioxide liquefied in the freezing-mixture (Fig. 146) and collects in
is

the U-tube as a green liquid (yellow if pure), oxygen passing on as

which the density is 14.4. It is neutral to litmus. gas
The smell of the gas is unknown because it combines with oxygen and escaping. Lead(II) oxide remains in the tube as a yellow solid
of the air (see tests above); it can never be collected by displacement fused into the glass.
of air.
2Pb(N0 3) 2 (c) -> 2PbO(c) + 4N0 2 (g) +O t (g)
 NITROGEN FIXATION 451
450 A NEW CERTIFICATE CHEMISTRY

r Properties of nitrogen dioxide

Nitrogen dioxide is usually seen as a reddish-brown gas, though
and molecules, the proportion of the latter increasing, as the
NOg
temperature rises to 150°C, when only NO. molecules are
present.
heat
the boiling-point of liquid nitrogen dioxide (22°C) is above the usual
N s O« ^ 2N0 2
atmospheric temperatures. It has a pungent, irritating smell and is a light yellow c°" 1
dark brown
rather dangerous gas on account of its tendency to set up septic dissociation, see p. 159.
For a more complete consideration of
pneumonia if inhaled. It should not be allowed to escape in quantity
into the open laboratory.

Action of nitrogen dioxide with water

THE IMPORTANCE OF NITROGEN COMPOUNDS
IN THE LIFE OF PLANTS
Pour a little of the liquid nitrogen dioxide prepared above into a
dry gas-jar in the fume cupboard and allow the liquid to vaporise. Fixation of atmospheric nitrogen
Add water and shake. The brown fumes dissolve leaving a pale blue The fertility of soil depends in part on the presence in the soil of
liquid. Add to blue litmus solution. The litmus is turned red. This
it certain chemical elements. These elements are potassium, nitrogen
is because the solution contains nitric and nitrous acids. and phosphorus, together with traces of iron, sulphur and others.

We shall consider, for the present, nitrogen alone.

2N0 2 -f- H 2 -> HNO s + HN0
nitric nitrous
8
Every time a crop taken from a given patch of soil, some of the
is

acid acid nitrogen previously contained in the soil is removed in the form of
The gas is a mixed anhydride. Similarly with sodium hydroxide, it complex organic compounds, which arc part of the tissue of the
gives a mixture of sodium nitrate and sodium nitrite. plant. This nitrogen was absorbed from the soil as dissolved nitrates
2NaOH + 2NO„ -> NaN0 3 + NaNO s + H 2 by the roots of the plant and this is the only manner in which the vast
sodium sodium majority of plants can absorb and use nitrogen. It is obvious that
nitrate nitrite unless nitrogen is continually supplied to the soil to balance the loss
suffered by removal of crops, the fertility of the soil will decrease and
Nitrogen dioxide as a supporter of combustion become meagre.
its yield
Like the other two oxides of nitrogen we have considered, nitrogen The some nitrogen by natural means. Certain plants,
soil receives
dioxide will support the combustion of a burning substance whose for example peas and beans, always have colonies of bacteria on their
flame is hot enough to decompose it and supply free oxygen. It will roots which are able to convert the nitrogen of the air into compounds
support, for example, the combustion of strongly burning phosphorus which pass into the soil. Electrical discharges in the atmosphere,

2P 4 + 10NO, - 2P O 4 10 + 5N, such as lightning, cause some slight combination of oxygen and
nitrogen and this leads to the passage of nitrogen into the soil as
but not that of sulphur or a candle.
nitrates, dissolved in rain water. This was a natural counterpart of
The use of nitrogen dioxide in the manufacture of sulphuric acid is now obsolete. Nitrogen-fixing
Birkeland and Hyde's process,
discussed on p. 411.
bacteria, living free in the soil, are another important agency supply-

Dissociation of nitrogen dioxide ing nitrogen to the soil from the air. Nitrogenous fertilisers are also
used to make good the loss of nitrogen. These fertilisers fall into the
At 150°C, nitrogen dioxide is very dark brown in colour. Its
following classes:
vapour density and its molecular weight is therefore 46, cor-
is 23,
responding to the formula NO, (N = 14; O 16). As the temper-= 1. Ammonium sulphate derived from the ammonia produced
ature falls, the vapour density of the gas gradually increases, until at when coal is distilled.
22°C it approaches 46, corresponding to a molecular weight of 92 2. Sodium nitrate from the deposits of this substance in Chile—
and a formula of N 8 4 At the same time it becomes lighter in
.
'Chile saltpetre', NaN0 3 .

colour. 3. Farmyard manure.

This must mean that, on heating, nitrogen dioxide dissociates, and, 4. Fertilisers produced by manufacture, using the nitrogen of the
fertilisers include ammonium sulphate, for which the
at any temperature between 22°C and 150°C, contains both
4 0« N air. These
 452 A NEW CERTIFICATE CHEMISTRY QUESTIONS 453

ammonia is prepared from nitrogen of the air by Haber's The nitrogen monoxide so formed is rapidly cooled and combines
process (p. 431), and nitrates, also obtained from nitrogen
of the with the oxygen from excess of air to form nitrogen dioxide.
air by oxidising ammonia to nitric acid. The nitrogen of the air
2NO + O, -*• 2NO,
is inexhaustible so that adequate supplies of nitrogenous
fer-
tilisers are now assured for ever. The nitrogen dioxide, in the presence of more air, is then absorbed in
hot water, the conditions being chosen to yield nitric acid by the
Though most plants can only use nitrogen as nitrates, it need not equation:
actually be supplied to the soil in this form. Bacteria in
the soil will 2H tO + 4NO„ -r- O s -> 4HNO s
carry out the oxidation of any nitrogen compound to nitrates
and the can be obtained by neutralising the acid with
plants can then utilise it. A valuable fertiliser

The sum total of lime and the calcium nitrate, mixed with excess of lime to form a non-
all these processes is called the 'Nitrogen cycle'.
A simplified deliquescent basic salt, is applied to the soil.
form of it isgiven in Fig. 147.
Ca(OH) 2 + 2HNO s ->- Ca(N0 3 ), i 2H t
Removed for food Ammonium sulphate
Loss of from coal
nitrogen Farmyard manure QUESTIONS
death and decay
plants -Ammonium compounds 1 Describe the usual laboratory method of making nitric acid, and give
an account of its action on (a) one base; (ft) one metal; (c) one
non-metallic
in the soil in the soil
element; id) one carbonate. (B.)
decay Haber's'*' acid,
process 2 Describe shortly how you would obtain, starting with nitric
specimens of (a) oxygen; (b) nitrogen monoxide; (c) dinitrogen oxide; and
(d) nitrogen dioxide. (N.U.J.B.)
Atmospheric nitrogen
3. Give equations illustrating the effect of heat upon nitrates.
Absorbed Describe concisely the properties of the gaseous products of these
Bacteria Haber's process oxidising
by or reactions. (O. and C.)
and oxidation bacteria
roots lightning ofNH 3 Describe the preparation and collection of nitrogen monoxide in the
4.
laboratory and give an account of its chief properties. How
would you
Nitrates from nitrogen prove that it consists of nitrogen and oxygen?
Explain, very briefly, how it is formed in the earth s atmosphere,
and
of the air
how the acid subsequently produced becomes 'fixed' in the soil as
indicate
nitrate. (B.)
Nitrates oxidising bacteria
in the soil "* 5 How would you prepare dinitrogen oxide? Give
an account of the
-Nitrites
properties and uses of this gas. Draw and describe the
apparatus you

Chile' / in the soil

would use to show that dinitrogen oxide contains its own volume of
nitrogen. (D.)
saltpetre
Three
NaNQ 3 6 Describe the preparation and properties of nitrogen monoxide.
litres of a mixture of nitrogen monoxide and
dinitrogen oxide were passed
Fig. 147. Calculate the
over red-hot copper, and 2.2 litres of nitrogen collected.
The nitrogen cycle. composition of the mixture. (O. and C.)
How would you prepare and collect some nitrogen monoxide free
7.

Haber's process for fixation of atmospheric nitrogen from nitrogen? .

Describe and account for what you would observe during the pre-
ferrous sulphate
Fixation of atmospheric nitrogen by Haber's process has already paration. What happens when this gas is (a) passed into
been considered (p. 431). solution, and (b) mixed with oxygen? (N.U.J.B.)
The product, ammonia, may be converted to ammonium sulphate 8. Given ammonium nitrate how would
you proceed to obtain a sample
417) or oxidised by passing the ammonia with excess of air over of (a) dinitrogen oxide; (A) ammonia? .

How would you obtain from ammonia a sample of nitrogen wnat is

(p. .'

platinum wire gauze (catalyst) at red heat ammonia and (a) iron(III)
the reaction between an aqueous solution of
4NH 3 + 50, -»• 4N0 + 6H aO chloride solution; (b) dilute sulphuric acid? (C.W.B.)
454 A NEW CERTIFICATE CHEMISTRY
9.How is nitrogen usually prepared and collected in the laboratory?
How is nitrogen obtained industrially?
Outline the industrial method by which nitrogen may be converted into
(a) ammonia; (6) nitric acid.
How and under what conditions does copper(II) oxide react with
ammonia? (N.U.J.B.) Chapter 35
10. You are provided with concentrated sulphuric acid, slaked lime,
ammonium chloride, potassium nitrate, water, a source of heat and any
apparatus needed, but no other chemicals. Explain briefly how you would
prepare (a) nitric acid, (b) ammonia solution, (c) quicklime, {d) pure dry
calcium sulphate. (N.U.J.B.) Phosphorus
11. Describe one experiment in each case to show that ammonia gas is
(a)very soluble in water and gives an alkaline liquid, (b) a reducing agent.
How, and in what conditions, does ammonia react with (/) chlorine, (//)
hydrogen chloride? How would you separate a sample of dry ammonia Occurrence
gas from a mixture containing this gas and nitrogen ?
PHOSPHORUS is a very active non-metal and is not found un-
12. Outline the Haber process for the fixation of atmospheric nitrogen. combined in nature. It was first isolated by Brandt, a Hamburg
How is the product of this fixation converted to two materials which can be
chemist, in 1669, who obtained it by distilling concentrated
urine
utilised as fertilisers for agricultural land? mineral phos-
with sand. It is extracted nowadays from bones and
13. State the volume composition of ammonia gas. Assuming the
matter from
diatomicity of nitrogen and hydrogen, deduce the molecular formula of phates. The residue left after burning away the organic
contains calcium phosphate, Ca (PO,) This substance also
ammonia, stating any principle of which you make use. How may am- bones 3 s .

monia be converted into (a) nitrogen; (b) nitrogen monoxide; (c) dry, occurs as the mineral, apatite.
crystalline ammonium chloride?

Extraction
contin-
A charge of calcium phosphate, sand and coke is fed
temper-
uously into an electric furnace, Fig. 148. At the very high
the high
ature obtained (the electric current is merely to produce

carbon
electrode

carbon electrode

Fig. 148.
Extraction of phosphorus.
455
r 456 A NEW CERTIFICATE CHEMISTRY PHOSPHORUS 457
temperature; there no
is electrolysis) the following reaction takes phorus and nothing else. Further, if equal weights of red and white
place:
phosphorus are converted fully to any given phosphorus compound,
2Ca 3 (P0 4) a + 6SiO + a 10C-* 6CaSiO a + 10CO +P 4
exactly the same weights of product are obtained.
calcium silicate
slag Comparison of allotropes of phosphorus
The phosphorus over with the carbon monoxide and the
distils
Red White (or yellow)
vapour is led below the surface of water, when the phosphorus
solidifies to a white solid. The calcium silicate is formed
as a molten
slag which is run off from time to time at A. Opaque red solid Colourless translucent solid
(turns yellow).
Chemistry of the action. Most salts can be considered as being made up 3 Density 1.8 g/cm 3
from a basic oxide and an acidic oxide. Density 2.3 g/cm . .

Non-poisonous. Very poisonous.

2Ca,(P04), = 6CaO.P O 4 I0
Sublimes at 400°C. Melting-point 44°C.
Silica is also an acidic oxide, hence Soluble in carbon disulphide.
Insoluble in carbon disulphide.
6CaO + 6SiO, — >- 6CaSiO, Ignites in air at 260°C. Ignites in moist air at 30°C.
calcium silicate Forms phosphine with hot
(cf. calcium carbonate) No action with hot sodium
The carbon hydroxide solution. sodium hydroxide solution.
(a reducing agent) reduces the oxide of phosphorus to
the
element. Unoxidised at ordinary tempera- Rapidly oxidised at ordinary
P 4 O 10 + 10C-»-P4 + 10CO tures in air.
temperatures in air.
On adding these equations together the main equation will be obtained.
White phosphorus is the unstable variety. It has the higher vapour
pressure and is very slowly reverting to red phosphorus in room
Allotropes
conditions.
Phosphorus exists in two chief allotropic forms, white or yellow Phosphorus is used in the match industry, in rat poisons and in
phosphorus and red phosphorus. The latter is the stable form. (See making smoke bombs. About 80% of it is converted to phosphoric
p. 457.) H 3P0 4
acid, .

Yellow phosphorus is a white solid which becomes pale yellow on

exposure to light It is of density 1.8 g/cm 3 and is soluble in carbon Match industry
disulphide. It smoulders in air owing to oxidation and this action
In earlier days, matches contained white phosphorus and an
causes it to glow in the dark.
oxidising agent and the mixture was caused to burn by rubbing on
P4 + 30 8 -»-P 4 8 sandpaper. The use of white phosphorus in industry caused hundreds
It is usually kept below the surface of water. Great care should be of work-people to suffer from phosphorus poisoning, which
took the
taken in handling it, for it gives off a very poisonous vapour and catches form of the rotting of the bones of the face and jaw ('phossy-jaw').
fire very readily. It burns in air or oxygen, giving off white fumes Its use was then forbidden by law and matches
nowadays consist of
of
oxides of phosphorus. This variety of phosphorus compounds of phosphorus (sulphides as a rule) and oxidising agents.
is formed when
the vapour of phosphorus is suddenly cooled. The friction of rubbing on a rough surface generates enough heat to
start the combustion. In 'safety' matches the phosphorus (red
variety)
Red phosphorus is the stable variety at all temperatures. It is not
poisonous as is yellow phosphorus, and does not catch fire so readily. is on the side of the box and thus the match-head, which contains the

It can be made by heating yellow phosphorus in an inert atmosphere oxidising agent, is useless without the box.
(usually with a little iodine to act as catalyst) to a temperature of
about 250°C. It is insoluble in carbon disulphide. Chemical properties of yellow phosphorus
Experimental evidence that the two allotropes are chemically Phosphorus combine readily with oxygen, chlorine and sul-
will
identical is the following. 1 g of white phosphorus heated to about phur. It is a reducing agent and readily attacks oxidising agents with
250°-300°C in an inert atmosphere yields exactly 1 g of red phos- the formation of oxides of phosphorus which are soluble in
water,
458 A NEW CERTIFICATE CHEMISTRY PHOSPHORUS 459

forming acids. It is attacked by alkalis forming phosphine. Phos- fumes owing to the action of moisture upon
in air it. The liquid is

phorus forms two series of compounds, exhibiting valencies of 3 and attacked by water, forming phosphorous acid.
5. For phosphorus in periodicity, see pp. 84-90.
PC1 3 3H,0 -» H 3 PO a + 3HC1
+
phosphorous
acid
Preparation of phosphine (phosphoretted hydrogen), PH 3
Fit up the apparatus as shown in Fig. 149 in a fume-chamber. Phosphorus pentachloride, PC1 6
Place sodium hydroxide (caustic soda) solution and a few trichloride by the action of chlorine
small This is made from phosphorus
pieces of yellow phosphorus in the flask, sweep out the air by out. It sublimes when heated,
means upon it. A yellowish solid separates
of coal-gas and warm the mixture. gas is given ofi", phosphine, and
A decomposing into the trichloride and chlorine, but on cooling
forms
on coming into contact with the air it ignites spontaneously
(the the original pentachloride.
heat

PCU PC1 3 + Cl»

cool
phosphorus phosphorus chlorine
sodium \ pentachloride trichloride

hydroxide
solution
\
(20%)
It also attacks water vigorously forming
phosphoric acid,
Pd + 4H aO -* H P0 + 5HC1
5 3 4

and yellow phosphoric

acid
phosphorus
Phosphorus trioxide (phosphorous oxide), P 40„
This in a limited supply of air and
made by burning phosphorus
water is

passing the mixture of trioxide and pentoxide through a tube sur-

50°C, and containing a loose cotton-
rounded by a water jacket at
remains solid and is retained by the plug.
wool plug. The pentoxide
The vapour passes on and is condensed in a freezing-
trioxide
mixture.
P« + 30 2 -»-P«0 4
Fio. 149. phosphorous
Preparation of phosphine. oxide

P« + 5O 1 -»-P«O l0
phosphoric
ignition is due to an impurity) and forms white vortex rings of oxides
oxide
of phosphorus.
Phosphorous oxide is a white volatile solid which readily reacts
3NaOH + P 4 + 3H a O-^ SNaHjPOj + PH 3 with water to form phosphorous acid.
sodium phosphine
hypophosphile P 40, + 6H aO ->- 4H P0 3 3
phosphorous
Phosphine a colourless gas with a garlic-like odour and is ex-
is acid
tremely poisonous. It shows similarities to ammonia, forming salts,
for example, PH 4 Cl,phosphonium chloride (cf. ammonium chloride). Phosphorus pentoxide (phosphoric oxide), P 4 O 10
plentiful supply of air A
Phosphorus This is made by igniting phosphorus in a
trichloride, PC1 3 a crucible on a plate of glass
small piece of phosphorus is placed in
This is made by
allowing dry chlorine to react with warm yellow under a bell-jar containing dry air. The phosphorus is ignited. It

phosphorus in an inert atmosphere. flame and a white solid finally settles on the
burns with a brilliant
P4 + 6CI 2 -* 4PC1 3 plate. This is quickly scraped into a
dry bottle.
Phosphorus trichloride is a liquid (boiling-point, 76°C) which P 4 -t-5O s -*P 4O 10
460 A NEW CERTIFICATE CHEMISTRY QUESTIONS 461

Itcan be purified by heating it in a current of dry oxygen. The Electrothermal reactions

latter convertsany trioxide formed into pentoxide. The extraction of phosphorus (p. 455) is an electrothermal reaction,
Phosphorus pentoxide is a white solid which reacts vigorously with that is, the current is used to produce heat and not for any electrolytic
water, and is one of the best drying agents known. With hot water it purpose. In such reactions, alternating current may be used; for
forms phosphoric acid. electrolytic decompositions, direct current is essential.

P«O I0 + 6H,0 -* 4H3PO4 Calcium carbide manufactured electrothcrmally. A steel furnace

is

phosphoric is used, lined with carbon, which acts as one of the electrodes. The
acid
other is a carbon rod, placed vertically. The furnace contains coke
Acids of phosphorus. Many acids of phosphorus exist, the chief of (carbon) and quicklime (calcium oxide). Alternating current causes
which are phosphorous and phosphoric acids.
arcing between the pieces of coke; this raises the temperature to
Preparation of phosphoric acid, H P0 from phosphorus about 2000°C.
3 4,

Heat a small amount of red phosphorus in a dish with fairly con- CaO + 3C -» CaC a + 2CO
centrated nitric acid (1:1, acid and water) for some time on a water Calcium carbide is produced molten, later cools to form a solid and
bath in a fume-chamber. Dilute with water and filter off any un- is broken up and graded in an atmosphere of
nitrogen to prevent
attacked red phosphorus. The product is a solution of phosphoric air-acetylene explosions.
acid, H3PO4. It may be concentrated, and any nitric acid removed, Calcium carbide is important chiefly because it yields acetylene,
by heating it till the temperature reaches 200°C, above which it C aH with cold water.
decomposes. The nitric acid is reduced to oxides of nitrogen and
there is a copious evolution of brown fumes during the experiment.
a,

CaC a + 2H O
a
- Ca(OH) a + C aH a
Acetylene is important as a source of polyvinyl chloride
(PVC)
The presence of a phosphate can be shown by warming a portion of
additively with acetylene to give
the filtrate with nitric acid and excess ammonium molybdate. A plastic. Hydrogen chloride reacts

yellow coloration or precipitate of ammonium phosphomolybdate vinyl chloride.

indicates the presence of a phosphate. HC3=CH + HC1 -> H,C=CHC1
P4 + 2OHNO3 -> 4H,PO« + 20NO + 4H O (the group H C=CH— a
called vinyl)
is
a a
phosphoric nitrogen and initiated
acid dioxide Vinyl chloride can be polymerised (in aqueous emulsion
PVC, which consists of long molecular chains of the
This acid, H
3 P0 4 , should strictly be called orthophosphoric acid; its
by peroxides) to
dehydrated product, HP0 3 , is metaphosphoric acid. type:

. .
. _CH s -CHCl-CH a-CHCl-CH -CHCl-CH a-CHCl- a
Phosphatic fertilisers
. . ._CH a-CHCl-CH a-CHCl-CH a-CHCl-CH a-CHCl-. .

Phosphorus is an element essential to soil fertility. Plants absorb it

(Compare the polymerisation of ethylene to polythene, p. 329.) PVC
from the soil and, if the crop is consumed by man, phosphorus and water-
is a thermoplastic much used in electrical insulation
passes into his bone structure and protoplasm. Much of it is lost to are lost in
proofing. Notice that the double bonds (unsaturation)
the soil in general by sewage disposal and by depositing human
polymerisation and PVC is a saturated compound.
remains in cemeteries.
The must be made good. Bone-meal and basic slag are used,
loss
both of which contain calcium phosphate, Ca^POJj. This com-
pound is, however, almost insoluble in water and becomes available QUESTIONS
A more soluble material, quicker in action,
to the plants very slowly. phosphorus from
Describe a method (a) for the preparation of white
1
can be made by stirring calcium phosphate with an appropriate phosphate; (b) for the conversion of white phosphorus into the red
calcium
weight of 65% sulphuric acid. An acid calcium phosphate is formed.
° contrast the properties of these two forms of
phosphorus.
Ca 3 (P0 4) 2 + 2H S0
a 4
->- Ca(H a P0 4 ) a + 2CaSO, Compare and
and with sodium
What reaction, if any, has each form with chlorine,
The product is dried and sold as 'superphosphate'. hydroxide solution? (D.)
462 A NEW CERTIFICATE CHEMISTRY
2. Compare the properties of the two forms of phosphorus. How may
phosphorus be converted into two of the following: (a) phosphorus penta-
chloridc; (6) phosphine; (c) phosphorus pentoxide? (O. and C.)
3. Describe with necessary detail how you would prepare from phos-
phorus reasonably pure specimens of (a) orthophosphoric acid (b) phos-
;

phorus trichloride. (O.)

4. Show by giving three chemical properties in each case that sodium
Chapter 36
is a metal and that phosphorus is a non-metal.
Starting with metallic sodium and yellow phosphorus, describe fully how
you would prepare specimens of (a) phosphine, and (b) sodium phosphate.
(L.) Metals; Extraction and Uses;
5. How does phosphorus react with (a) oxygen; (b) chlorine; (c) sodium
hydroxide? Non-Metals Compared
Describe how the products behave when brought into contact with
water. (O. and C.)
recently, physical differences between metals and non-
6. Describe the preparation of (a) phosphorus trichloride, and (b)
UNTIL
metals have been regarded as quite significant. For example,
phosphine. Show how the latter is related to ammonia. (L.)
gold and silver, with high density, lustre, malleability and ductility,
7. How is phosphorus obtained from bone ash? State how white
phosphorus can be converted into red phosphorus, and name three have been regarded as two of the most typical metals; sulphur, which
respects in which they differ from one another. Write the formula; of two has a much lower density and no lustre, and is very brittle, was
chlorides, one of hydride, and two oxides of phosphorus. How does the regarded as a typical non-metal. This outlook has been largely
highest oxide of phosphorus react with water and for what purposes is this
replaced by the following:
oxide used ? (L.)
8. Contrast, tabulating your answer, six properties of two allotropes of
phosphorus. Starting with one of these forms, briefly describe the pre- METALS
paration of the other form from it. How is phosphine usually prepared in
the laboratory? Give details. (L.) A metal is defined as an element which can ionise by electron
now
loss. The number of electrons lost per atom is the valency of
the metal

and the ion carries an equal number of positive charges, as:

Na — e
- —> Na + (univalent)

Mg-2e~-»-Mg 2+ (divalent)

Al — 3e~—* Al 3+ (trivalcnt)

The following are important chemical properties of metals which

are derivative from this ionisation behaviour.

1. The oxide of a metal is basic, and, if soluble in water, gives an

alkaline solution.

This property follows from the fact that a typical metallic oxide
is formed by oxygen accepting electrons
from the metal as it ionises,
2- For example,
to form the ion, O .

Ca-»-Caa+ + 2ei
"}
iO g + 2e--*-0 2 -
or adding these, Ca + iO, -* Ca» + 0*~
If the oxide dissolves in water, it gives the
reaction:

O 2-
+ H,0 e* 20H-
characteristic of alkalinity. If
so providing the hydroxyl ion, which is

463
 :

464 A NEW CERTIFICATE CHEMISTRY METALS 465

insoluble in water, the oxide does not produce alkalinity but acts as Such chlorides are electrovalent, electrolytes when molten or in
a basic oxide. aqueous solution, and solids of very low volatility.
This property arises from the behaviour of the 8- ion or ion O OH~
with hydrogen ion, , H
+ which is characteristic of acidity.
The 4. Metals form few compounds with hydrogen
behaviour is:
This situation arises because hydrogen forms compounds most
O 2 - + H,0 f* 20H-"!
readily by covalency (i.e., electron sharing) or, in acids by electron
20H- + 2H + ^2H 8 OJ loss, to form the ion, H+ Neither of these modes of combination is
.

The second of these reactions

the essential nature of neutralisation,
is
well suited to metals, which tend to operate by electron loss.
-
i.e., the formation of water from its ions, + and H
The ions, OH .
A few very powerful metals (Na, K, Ca) can force hydrogen to
Ca 2+ and 2CI~, derived from calcium oxide and hydrochloric acid accept electrons.
may remain as the salt, calcium chloride, and correspondingly for The hydrides so formed are salt-like solids (compare the chlorides
other oxides and acids. The complete reaction can be represented as: above) and liberate hydrogen with cold water, e.g.,
Ca* + 8 - + H aO ^ Caa+ (OH-) 2 Na ±H,-»-Na + H-
+
Ca +(OH-), + 2(H + C1")
a
-> Ca2+ (Cl-), + 2H 2 H- + H 20-*OH- + H,
2. A metal can replace H+ ion in an acid and so produce a When molten, they act as electrolytes and liberate hydrogen at the
salt
anode.
This replacement may occur directly or indirectly. If directly, the
H--e--*iH a
metal ionises, liberating electrons; the electrons are accepted by + H (to anode)
ions in the acid. These ions become hydrogen atoms, pair off as H+ hydrogen appears
In aqueous solutions, containing the usual ion, ,
molecules and are liberated as gas. The metallic ions pass into
at the cathode during electrolysis.
solution and, in conjunction with the negative ions of the acid, CI~,
S0 4 2_ etc., constitute a salt. For example H+ + e-->iH,
(from
Zn-».Zn 3 + + 2e-\ cathode)
2H + + 2e~ -> H 2 J
For dilute sulphuric acid, 5. Metals are reducing agents
Zn + (H + ),S0 4 *- ->- Zn s+ SO« - + 2
H, This follows from the modern definition of a reducing agent (p.

162) as an electron donor, e.g.,

Indirect replacement occurs chiefly through the medium of the
metallic oxide or hydroxide, as: K-»-K+ + e-
2-
Zn ->- Zn2+ + 2e~
+ K) t -»-Cu* +
Cu
O*- + H,0 5* 20H- Fromthe theoretical angle, the most characteristic physical pro-
20H- + 2H+ ^ 2H,0 perty of a metal is its ability to conduct electricity, i.e., to pass a
If the acid is dilute sulphuric, Cu 2+ ions are left in solution, with
stream of electrons through itself if a potential difference is applied
across it. This arises because metallic atoms part with
electrons easily
S0 4 2 ~ ions, as the salt, copper sulphate, the
other product being water.
and a mass of metal always contains comparatively loose electrons.
3. Metals form elect rovalent chlorides. These move readily through the metal and are steadily replaced from
Metallic chlorides are typically electrovalent in type because, in the source of potential difference to maintain a flow of current. Con-
their formation, a metal loses electrons, which duction of heat, lustre, malleability, ductility and high tensile
are accepted by
chlorine atoms, e.g., strength are other physical properties possessed by some metals. They
are very useful in practice but are not now accorded their former
Ca ->- Ca 2+ + 2e-\ importance. Many metals have high density, but the most charac-
CI, + 2e- ^ 2CI- / teristic common metals, i.e., those which ionise most readily by
or adding these, Ca + CI, — >- Ca2+ (C1-), electron loss, are sodium and potassium, and they have densities
 H P

466 A NEW CERTIFICATE CHEMISTRY NON-MBTALS 467

below that of water. They are also soft enough to be cut with a pen- an acid to form a salt (as a
knife.
2. A non-metal never replaces hydrogen in

metal does)
Replacement of hydrogen in an acid arises from the acceptance by
NON-METALS H + of electrons supplied by a metallic atom:
If a non-metal forms does so by electron gain, i.e., the element
ions, it 2H + + 2e~ -* H 2

is electronegative. The number of electrons gained per atom is the and so cannot bring about the
A non-metal is an electron acceptor
valency of the element for this purpose. (It may also exercise other
above replacement.
kinds of valency.) The ion formed carries the corresponding number
of negative charges but they never exceed two. Non-metals form covalent chlorides
3.
|CI 3 + e~ -* CI-- (univalent)
The behaviour of the non-metal, phosphorus, in forming its
£Br 8 + e~ —* Br - (univalent) trichloride is typical.
±b 8 -f 2e~ —>- O8 (divalent)
S + 2e--»-S a - (divalent) CI
o«
CI
The following arc important chemical properties of non-metals ° I

CI* CI— • electrons from CI

which are connected with their tendency towards electron gain, U1
o Pr o or
O electrons from P
o« k
1. The oxide of a non-metal never basic. Its characteristic oxide
is is CI
acidic. Its other oxides are acidic or neutral
Each CI atom has also seven more electrons (not shown) in its outer
As explained on p. 464, a basic oxide is formed when an oxygen electron layer. A
covalent chloride of this kind is usually a volatile
8-
atom accepts electrons from a metallic atom to give the ion, O .
liquid, a non-electrolyte, and rapidly hydrolysed by
water, as:
Since a non-metal is an acceptor of electrons, it cannot form an oxide
in this way. The characteristic oxide of a non-metal, i.e., the oxide in
PCl a + 3H gO -> H 3PO s + 3HC1
which the non-metal exercises its maximum valency, is a covalent These properties are characteristic of non-metallic chlorides (though
oxide, produced by formation of shared electron pairs. CC1 4 is not hydrolysed by water). Non-metals cannot supply electrons
to form electrovalent chlorides. This is the
behaviour of metals
When combined with water, it forms an acid, e.g.,
(p. 464).
Maximum
Non-metal Characteristic oxide: action with water
valency its
4. Non-metals combine with hydrogen to form many covalent hydrides
Carbon 4 co, +ho^h 8 8 co, ^ 2H+ + co,»-- These hydrides are formed by electron sharing, as:
Nitrogen 5 N O + H8
a B
?s 2HN0 3 ^ 2H + + 2NO - a
Sulphur 6 S0 3 + HgO ?± H 3 SO« ^ 2H+ + S0 2 (Each bond represents one shared pair of electrons)
4
Chlorine 7 C1 2 7 + H O ^ 2HCI0
a 4 ^ 2H+ + 2C10«- H H H
The H
When
ion, characteristic of acidity, is produced in all these cases.
H— C— A-H \ h—a
sometimes
the non-metal exercises a reduced valency, the oxide
sometimes neutral, but never Examples:
is 1

1
1

H
/
acidic, basic.
H
methane ammonia hydrogen sul- hydrogen chlorid
Non-metal Oxide Nature of oxide phide (covalent (covalent form)
Carbon CO neutral form)

Nitrogen N8 neutral
Simple hydrides of this type have the properties of covalent com-
N aO« acidic
pounds; they are gaseous, form no ions when anhydrous and so are
Sulphur S0 8 acidic
non-electrolytes. Salt-like hydrides are formed by metals (p. 465) but
Chlorine C1 2 acidic
non-metals cannot supply the electrons required for this.
 : : : .

468 A NEW CERTIFICATE CHEMISTRY METALS 469

wrt
5. Non-metals are oxidising agents
This follows from the modern definition (p. 162) of an oxidising
agent as an acceptor of electrons, e.g.,
iCl s + e--*-C\-
S + 2e~ -»- S a ~
The most important physical property of non-metals is their very
low electrical conductivity. Because of the tendency of a non-metal to
attract electrons, a mass of it contains an absolute minimum of free
electrons. This being so, no considerable electron flow can occur
through the non-metal and it tends to be a very poor electrical
Wft
conductor. (Graphite is exceptional, conducting electricity quite
well.) In addition, non-metals are usually brittle and do not give sheets
or wire. They have low tensile strength and no lustre, and cannot be
polished.
To summarise in tabular form

K
iL tk n la Hi M CataAuCu T»
METALS NON-METALS Fio. 150.
Melting-points of the common metals (excluding mercury). The metals are
Chemical Properties represented by their symbols.
Metallic oxides are basic and Characteristic oxides of non- shows an important between certain
The following table relation
form alkalis if soluble in water. metals are acidic; other oxides
properties of metals and non-metals.
are acidic or neutral.
Metals replace hydrogen in acids Non-metals do not form salts in
ELEMENTS
forming salts. this way.
Metallic chlorides are electro- Non-metallic chlorides are cc-
valent salts, electrolytes con- valent, non-electrolytes, and
taining Cl~ ions. are generally hydrolysed by
METALS NON-METALS
water.
Metals form few stable hydrides. Metals form oxides Non-metals form
Non-metals form many stable
which are oxides which are
Na, K and Ca form salt-like hydrides; they are covalent,
hydrides, which contain ions, the simple ones being gases
BASIC OXIDES ACIDIC
H-. (like NH 3 or CHJ and non-
electrolytes if water-free.

Physical Properties
Metals are Non-metals are A few basic oxides Acidic oxides
are soluble in water combine with
good conductors of electricity generally bad conductors of
and form water forming
and heat; malleable (can be electricity and heat (graphite
beaten into sheets); ductile conducts electricity well); gen-
ALKALIS ACIDS
(can be drawn into wire); erally brittle, not malleable or
metals"]
lustrous and can be polished. ductile;
Some metals are very dense and generally not lustrous.
basic oxides > + acids
alkalisj
have high tensile strength.
form

SALTS
470 A NEW CERTIFICATE CHEMISTRY POTASSIUM, SODIUM 471

EXTRACTION OF METALS FROM THEIR metal in ionised condition. During extraction, the metallic ion takes
NATURALLY OCCURRING COMPOUNDS, PRO- up the necessary number of electrons to convert it to the correspond-
ing atom. This process of electron gain is a reduction and the electrons
PERTIES AND USES OF THE COMMON METALS
are supplied by the reducing agent concerned in the reaction. For
Extraction and the electrochemical series 2+
example, in the ore, galena, Pb .S*~, lead exists (as shown) in ionic
K form. After extraction, it exists as atoms of lead. Therefore, at some
Ca stage, the change:
Very reactive. Never found as free element. Extracted
Na
'electrolysis. All isolated after 1800.
by
Pb2+ + 2e~ —* Pb (a reduction)
Mg place. The electrons arc supplied when the reducing
must have taken
Al
agent, carbon, acts upon lead oxide, produced as an intermediate
Zn
product in the extraction.
Fe
Pb O 2 - + C -»- CO + 2e-
Cu The reduction of the first members of the series is
in the case
Hg Not very reactive. May be found in nature as the free brought about by electrolysis, which can be regarded as a very power-
Ag element. Known for a very long time. ful oxidation and reduction process which often results in the forma-
Au tion of the elements present in the compound electrolysed (see
In this chapter the physical properties of the metals are arranged Electrolysis, p. 133). As far as the metals are concerned the process
in the same order throughout. The electrochemical series shown is one of reduction, although no reducing agent (in the ordinary sense

above indicates (in a very rough way only) the inverse order in which of the term) is used.
the elements were isolated. Thus metals low in the series such as The cathode acts as a reducing region by supplying electrons. The
gold, silver and lead have been known since very early times. Metals usual reducing agents employed for the less electropositive metals are
high in the series proved very difficult to isolate and it was Davy's carbon in the form of coke, and carbon monoxide (made from the
work on electrolysis which led to the isolation of potassium, sodium, coke by passing a limited amount of air over the hot coke). You may
calcium, magnesium and aluminium over a period of years from 1807 ask why the usual laboratory reducing agents are not employed ; for
(when Davy isolated potassium and sodium) to about 1850 (when example, hydrogen. The reason is that, in an industrial process the
aluminium was isolated). chief concern is cost, and coke easily wins on that score.

Aluminium was not obtained in the first place by electrolysis

although its manufacture nowadays is entirely confined to that
method, but it was isolated by the action of the very active element
POTASSIUM AND SODIUM
potassium on aluminium chloride. Occurrence
In view of what we have learnt about the electrochemical series, These metals occur chiefly as the chloride, sodium as common salt
this order seems quite natural for we should expect the compounds in the huge salt deposits of Cheshire, and elsewhere, and potassium
of the very active elements such as sodium and potassium to be very chloride as carnallite (together with magnesium chloride) in the
stable substances. deposits in Stassfurt (see p. 376). Other sources of the elements are:
Metals low down in the scries are frequently found as the free
sodium carbonate in Africa and in ash of sea plants.
elements, although they may also be obtained from ores because the
sodium nitrate Chile saltpetre in Chile.
amounts found as the free metal are not sufficient for industrial
sodium chloride in sea-water and many salt lakes.
purposes. Gold, however, the last clement of the series, is found and
potassium nitrate saltpetre found in India.
mined almost entirely as the free element.
potassium carbonate in the ash of land plants.
Extraction is a reduction
Potassium
Metals are found as a rule as their oxides or salts, chiefly sulphides
and carbonates, which are electrovalent compounds and contain the Potassium is obtained by the electrolysis of its molten hydroxide.
472 A NEW CERTIFICATE CHEMISTRY SODIUM 473
Physical properties of potassium At the cathode At anode
the

State Solid. Na+ + -

e _>. Na OH- - e~ -»- (OH)
Appearance Then: 4(OH) -» 2H tO + O,
White metal, possessing a lustre.
3
Density 0.86 g/cm- .

Malleability Malleable and ductile.

Tensile strength Does not possess tensile strength to any
appreciable extent
Melting-point 63°C.
Conduction of heat
and electricity Good conductor of heat and
FUSED
electricity. Caustic Soda
In chemical properties potassium is very similar to sodium, but it is Causae Soda
slightlymore reactive. Thus, when a small piece of potassium is solution)

placed on water it darts about, melts and gives off hydrogen which at
once ignites and burns with the oxygen of the air, giving a lilac-
coloured flame.
2K + 2H 2
-»• 2KOH + H,
Flame tests for potassium (see p. 374)
Compounds of potassium (especially the chloride) colour the
Fig. 151.
Bunsen flame lilac and the colour is still visible through blue glass. Preparation of sodium.
Hence, although the lilac colour of potassium is easily
masked by the presence even of traces of sodium, the Industrial extraction of sodium (Downs process)
potassium colour is visible when viewed through blue glass. In this process, common salt is electrolysed in the molten condition.
In general, the salts of potassium are less soluble in water than the As the melting-point of the salt is high (about 800°C), calcium
corresponding salts of sodium (the principal exceptions are potassium
Sodium chloride odded
hydroxide, potassium carbonate and hydrogen carbonate). This
accounts for the use in medicine of such substances as potassium
permanganate, potassium iodide, potassium chlorate, where one Fused sodium
chloride and
would expect the cheaper sodium salt to be used. The extra cost of calcium chloride
preparing the potassium salt instead of the cheaper sodium salt is
outweighed by the ease of obtaining the potassium salt from the
solution because of its lower solubility.

Extraction of sodium
Iron
Sodium was first isolated in 1807 by Davy. He electrolysed caustic caihode Irongauze
diaphragm
soda between platinum electrodes, obtaining small beads of sodium
metal at the cathode. A more suitable version of this extraction is
illustrated by Fig. 151. Note that the electrolyte is molten caustic Carbon
soda, i.e., solid caustic soda heated till it liquefies. If water were anode
present, sodium could not be produced. The caustic soda (sodium FlQ. 152.
hydroxide) gives the ions, Na* and OH". Extraction of sodium from common salt.
474 A NEW CERTIFICATE CHEMISTRY CALCIUM 475

chloride is added to lower the melting-point; it becomes about If a light is applied the hydrogen given off will burn with a goMen-
600°C. The Downs cell(Fig. 152) has an outer iron shell, lined with yellow flame. Sodium and potassium are so readily attacked by the
firebrick. A diaphragm of iron gauze screens the carbon anode from oxygen and water-vapour of the atmosphere that they are usually
the ring-shaped iron cathode that surrounds Chlorine escapes via
it. kept below the surface of petroleum oil.
the hood. Sodium collects in the inverted trough, T, placed over the
cathode, rises up the pipe, P, and is tapped off through the iron Flame coloration
vessel, V. Sodium chloride produces ions Na + and Cl~. Sodium compounds impart a persistent golden-yellow coloration

At the cathode At the anode to the flame (see flame-test, p. 374). This colour is invisible when
Na + + e--*Na C\--e~—»-CI viewed through blue glass. The above serves as a very definite and
(a reduction) (an oxidation) delicate test for the presence of sodium in a compound.
Then: CI + CI -+ CI, Uses of sodium
Physical properties of sodium
Sodium is used in the manufacture of sodium cyanide, NaCN,
State Solid.
which is employed in the extraction of gold, and also in manu-
Appearance White, silvery, shining metal. Rapidly
facturing sodamide, NaNH., and sodium peroxide, Na s O,. An alloy
tarnishes.
of sodium and lead has been employed in the manufacture of lead
Density 0.97 g/cm-3 .
tetraethyl, an anti-knock additive used in petrol.
Malleability Very malleable. Can be cut with a knife.
Tensile strength Does not possess tensile strength to any Pb + 4Na + 4C,H 6C1 ->• 4NaCl + Pb(C,H 8 )4

appreciable extent. The alloy heated in ethyl chloride vapour. Sodium vapour lamps
is

Melting-point 98°C. are well known for the intensely yellow illumination they give.
Conduction of heat Sodium has also found a recent use in the reduction of titanium
and electricity Conducts both heat and electricity. chloride to the metal by heat. Titanium is used in high-temperature
steels.
Action of sodium on exposure to air TiCl 4 + 4Na-»- Ti + 4NaCl
Sodium is attacked by the oxygen of the air to form sodium oxide.
The moisture present combines with some of the oxide to form the CALCIUM
hydroxide and finally, after a time, the carbon dioxide of the air com- Occurrence
bines with the sodium hydroxide to form sodium carbonate.
Calcium occurs abundantly and very widely distributed as
+ 0„-*-2Na 1
4Na calcium carbonate, CaCO a, which is found as chalk, limestone,
Na + H O -»• 2NaOH
2 a marble, calcite, Iceland spar and aragonite.
2NaOH + C0 ->- Na 2C0 3 + H O
2 t It also occurs as calcium sulphate as gypsum, CaS0 4
2H,0, and .

If heated in air or oxygen, sodium burns with a golden-yellow flame as anhydrite, CaS0 4 .

to form sodium peroxide. It occurs, less abundantly, as

fluorspar, calcium fluoride, and as

2Na-| 0,-»-Na 2O s calcium phosphate.

Action of sodium on water Extraction

Calcium obtained by the electrolysis of fused calcium chloride.
is
Place a small piece of sodium (a piece the size of a very small pea
will be ample) on the surface of water in a large dish or trough. The (Notice that whereas potassium is obtained from the hydroxide,
sodium will dart about and melt to a silvery ball of molten sodium, calcium cannot be obtained from the hydroxide by electrolysis. The
liberating hydrogen and forming sodium hydroxide (see p. 196). reason is that if calcium hydroxide is heated strongly it becomes
quicklime and, if that is heated strongly, it merely becomes white hot
2Na + 2H gO -»- 2NaOH + H, and does not melt. Quicklime is one of the most refractory sub-
sodium
hydroxide stances known.)
476 A NEW CBRTIFICATB CHEMISTRY ALUMINIUM 477

Calcium chloride, which is obtained as a by-product from the A white film of oxide is formed on the surface on exposure to air.
Solvay process (see placed in a graphite (carbon) container
p. 3 10), is Calcium will burn with a brick-red flame if heated in the air and
which is the anode of the cell (Fig. 153). The cathode is an iron rod forms quicklime, calcium oxide.
which just dips below the surface of the calcium chloride. The calcium 2Ca + O -* 2CaO
s
chloride is melted and the electrolysis is begun. As the calcium forms
Action of calcium on water (see p. 196)
-Cathode
Calcium attacked by water, liberating hydrogen and forming a
is

solution of calcium hydroxide.

Ca -f 2H s O -> Ca(OH) g + H,
The action not so vigorous as that of sodium or potassium and a
is
+ Anode be placed over a piece of calcium in
test-tube full of water can safely
a dish containing water, and the hydrogen can be collected.

Flame coloration (see p. 374)

Calcium compounds (especially the chloride) colour the flame

~<Z--=--^=r-^-7/-^Graphita brick red.

FlO. 153. Uses

Extraction of calcium. Calcium is used as a dcoxidiscr for steel castings and in the
extraction of thorium by heating its tetrachloride with calcium.
on the iron rod, the latter is withdrawn and an irregular stick of cal-
cium is gradually formed. Chlorine is evolved at the anode. If the
ThCl 4 + 2Ca -> Th + 2CaCl a
anode were made of metal it would be attacked by the chlorine, but
chlorine has no effect on carbon, and the gas is a valuable by-
ALUMINIUM
product. Occurrence
At the cathode At the anode Compounds of this metal are quite abundant. Some of the better
Ca»+ + 2e~ -»- Ca 2C1" - 2e~ -»- CI, known are:
(a reduction) (an oxidation)
Mica, felspar, K
2 AljSi g O, 9
Physical properties of calcium
Kaolin (china clay), Al 2 Si 20,.2H 2 (used in making porcelain)
State Solid. Corundum, A1 2 3
Appearance Silvery, shining metal which rapidly Cryolite, Na 3 AIF,
tarnishes in air owing to formation of Bauxite, AU0 3 .2H 8
film of oxide.
Density 1.55 g/cm-».
Extraction
Malleability Malleable and ductile. Purified bauxite (alumina, Al a 3) is electrolysed (Fig. 154) in
Tensile strength Possesses fair tensile strength. solution in molten cryolite. If more added as
purified bauxite is

Melting-point 850°C. required, cryolite is unchanged and can be used indefinitely. Pure
Conduction of heat aluminium is tapped from the cathode, but the carbon anode tends
and electricity Good conductor of heat and electricity. to be oxidised away by oxygen.
2A1 3+ + 6e- -»- 2AI ; 30 2 ~ - 6e~ -»- 1 iO a
Action of air on calcium
at at
Calcium is not as reactive as sodium and potassium, and it is not cathode anode
necessary to keep it below the surface of petroleum. Cryolite is sodium aluminium fluoride.
 478 A NEW CERTIFICATE CHEMISTRY EXTRACTION OF MBTALS 479

+, carbon anode Action of aluminium with caustic alkali solution

Crust of solid
electrolyte carbon lining The metal, especially in powder form, reacts violently with bench
as cathode sodium hydroxide solution, liberating hydrogen and leaving sodium
aluminate in solution. (Potassium hydroxide similar.)

pure aluminium oxide 2A1 + 20H- + 6H 8

- 2Al(OH)," + 3H 8

in molten cryolite steel trough Uses of aluminium

(1) In alloys. The metal is a constituent of several light alloys.

They combine high tensile strength with lightness, and have been
Molten aluminium much used in aircraft construction. Duralumin (Al, Mg, Cu, Mn),
Fig. 154. magnalium (Mg, Al) and aluminium bronze (Al, Cu) are well known.
(2) In cooking utensils. Cheapness, low density, good appearance,
Extraction of aluminium.
good conductivity for heat and resistance to attack by cooking
solutions have combined to make aluminium very popular in the
Physical properties of aluminium kitchen. Aluminium vessels must not be exposed to alkaline solutions
State Solid. (see above).
Appearance Silvery white. (3) In overhead electric cables. The lightness
of aluminium is very
Density 2.69 g/cm-3 . favourable here. Thick cables of low resistance can be employed
Malleability Can be rolled into foil. without undue weight.
Tensile strength Moderate (high in alloys). (4) In aluminium paint. The powdered metal is used, with oils.
Melting-point 660°C. (5) In thermit processes.
The reactions between aluminium powder
Conduction of heat and electricity Good. and oxides of other metals are commonly very exothermic. If a
mixture of iron(IH) oxide and aluminium powder, known as 'ther-
Action of aluminium with air mit', is 'fired' by burning a piece of magnesium ribbon stuck into it, a
violent reaction will occur. Molten iron is produced with a slag of
The metal acquires a continuous, very thin coating of oxide and
aluminium oxide floating on it.
this resists further action. At 800°C, it will burn in air, forming its
oxide and nitride.
Fe 2 8 + 2A1 -»- 2Fe + A1 2 8

This reaction has been used in welding steel parts in situ by means
4A1 + 30 2 2A1.0,
of the molten metal produced, and in incendiary bombs in the early
2AI + N,- 2A1N.
part of World War II. Similar reactions are also used in isolating
certain metals, e.g., chromium.
Action of aluminium with acids
Cr a 3 + 2A1 -> 2Cr + A1 2 3
The metalattacks dilute hydrochloric acid slowly and the con-
centrated acid rapidly, liberating hydrogen.
GENERAL IDEAS ON EXTRACTION OF METALS
2A1 + 6HCI -*- 2A1C1 3 + 3H,
FROM THEIR ORES
Aluminium has no action with dilute sulphuric acid, but the hot,
concentrated acid The four metals already described are obtained from their com-
is attacked by itwith liberation of sulphur dioxide.
pounds by electrolysis. We
now come to those metals which have been
2A1 + 6H 8 SO, -» A1 2 (S0 4 )8 + 6H.0 + 3S0 8 obtained for manyyears and which are used in far greater quantities
aluminium at any concentration. This
Nitric acid does not react with than the more electropositive elements.
is probably becauseproduces on the metal a thin layer of insoluble
it
oxide, which protects the metal from further attack. (See passive
The metals zinc, iron, lead and copper are found chiefly as the
impure carbonates and sulphides, and iron is also found as the
iron, p. 488.)
impure oxide. The following processes are amongst those commonly
480 A NBW CERTIFICATE CHEMISTRY ZINC 481

used in the extraction of metals from their ores although all the The ores are first roasted in air when the oxide is formed whether
processes are not used in connection with each individual metal. the ore is calamine or zinc blende.

Concentration of ores ZnCOs-^ZnO + CO,

Very often, as ores are found contaminated with earthy impurities,
2ZnS 4- 30 3 -* 2ZnO + 2SO,
methods are employed to pick out the richer ores, or those worth The sulphur dioxide is frequently used for the manufacture of
working up, and to reject the poorer grades. This may be done by sulphuric acid.
hand, or the earthy matter may be washed away by means of a stream The ore is now mixed with coke and placed in a fireclay retort to
of water, leaving the heavier ores. In the case of copper ores, the the end of which there is attached a fireclay condenser (Fig. 155). On
latter drop through a magnetic separator where metallic ores are
retort
deflected into one pile, whilst the lower-grade ores and earthly im-
purities are not deflected and pass straight on.

Roasting in air 'Iron

prolong
Since many ores contain either the sulphide or carbonate of the
metal, a preliminary roasting in air will remove the sulphur as sulphur Furnace wall
ft/mace
dioxide and drive off carbon dioxide from the carbonate. Thus:
Fio. 155.
2ZnS(c) + 30 2 (g) -* 2ZnO(c) + 2SO,(g) Extraction of zinc.
ZnCO (c) -> ZnO(c) + CO (g)
a z

The oxides are usually easier to deal with than the sulphides or the end of this condenser is placed an iron 'prolong' which collects
carbonates. any zinc which escapes the condenser. The mixture is heated by
means of producer-gas for about twenty-four hours. The zinc oxide
Reduction process isreduced to metallic zinc, the carbon becoming carbon monoxide,
The roasted ore must now be reduced. The reduction in the case of which burns at the mouth of the condenser.
zinc and iron is by means of carbon. In some cases (e.g., copper), by ZnO +C
carbon
- Zn(g)
zinc
+ CO
carbon
a suitable adjustment of the roasting process, it is possible to oxidise zinc
oxide monoxide
some of the sulphide to oxide, and then by adding more of the ore to
supply sufficient sulphide to react with the oxygen of the oxide, The zinc distils out of the retort and the bulk of it condenses to
leaving the metal. molten zinc in the condenser, and is removed from time to time.
Owing to the presence of air in the retort, some of the zinc burns to
Purification zinc oxide and condenses on the upper part of the condenser as 'zinc
The product of the reduction process is seldom a pure specimen of dust' (this is a mixture of zinc and zinc oxide). The impure zinc
the metal. Purificationmay be carried out electrolytically (as in the obtained in this way is purified by electrolysis. It is frequently
case of copper and zinc). By electrolysis a very pure product is 'granulated' by running the molten metal into water. (In this granu-
usually obtainable. In other cases the impure metal is heated in a lated form the zinc offers a larger area for action with, e.g., dilute
hearth open to the air, when impurities oxidise and rise to the surface acids.) See also p. 155.
as a scum and can be removed.
Physical properties of zinc
ZINC State Solid.
Occurrence Appearance Bluish-white metal. Can be polished.
Density 7.1 g/cm" 3 .

Zinc occurs in various parts of the world, as

Malleability Malleable at temperatures between 100°
Zinc carbonate, ZnCO a , calamine, and
and 150°C.
Zinc sulphide, ZnS, zinc blende. Possesses high tensile strength.
Tensile strength
482 A NBW CERTIFICATE CHEMISTRY IRON 483

Melting-point 419°C. Uses of zinc

Conduction of heat Galvanising. Small iron objects and iron wire or sheet are often
and electricity Good. coated with zinc (i.e., galvanised) to delay rusting. This may be done
by spraying, electrolytic deposition or dipping into molten zinc. Zinc,
Action of zinc on exposure to air in air, acquires a coherent, inert oxide layer by which rusting of the

Zinc is only very slightly attacked by air owing to the formation of iron is prevented. Also, some protection is still given to the iron even
if the zinc layer is broken. This is so because zinc is more
electropositive
a film of oxide which prevents further action. If heated in air, it will i+ —
burn with a bluish-green flame forming the oxide. than iron and the first stage of oxidation of zinc, Zn * Zn 2e~, +
occurs in preference to that of iron, Fe * Fe* —
+ 2e~. +
2Zn + O a -> 2ZnO Thin iron sheet can also be tin-plated by passing the cleaned sheet
through molten tin with a flux present, e.g., zinc chloride. Tin-plate
Action of acids isused in canning fruit, meat and fish (to which it imparts no taste).
Ordinary samples of zinc are attacked readily by .the mineral acids. A continuous layer of tin protects iron from rusting (being unreactive
Very pure zinc is only slowly attacked, and in recent years the purity with air). Tin, however, is less electropositive than iron, so, as soon
of even the commercial zinc is so high that very often the action of as the tin layer is broken, oxidation of iron begins.
dilute sulphuric acid on zinc is slow at first. The common actions are Zinc is also used in alloys, e.g., brass (copper and zinc, 2 1) and :

expressed by the equations: in dry Leclanche batteries, as the negative pole.

Zn + H S0 s 4
- ZnS0 4 +H 2
zinc dilute zinc hydrogen
sulphuric sulphate IRON
acid
Occurrence
With hot concentrated sulphuric acid, sulphur dioxide is formed.
The occurrence of iron, a metal of immense importance, has had a
Zn + 2H 2 S0 4 -»- ZnSO, + 2H 2 + SO, profound effect upon the development of the countries in which it is
Zn + 2HC1 ->- ZnCl a +H s found. Your geography book will tell you how important it has been
zinc dilute zinc hydrogen necessary for the
hydrochloric chloride to this country that iron ore and coal (which is
acid extraction of large quantities of the metal) have been found com-
The are the following:
3Zn + 8HN0 3
-»- 3Zn(N0 3) 2 + 4H O + 2NO
a
paratively close together. chief ores
zinc Hamatite, found in Great Britain, United States, France, Germany,
nitrate
Belgium and Spain, is impure iron(III) oxide, Fe.0 3 .

(In the last case other oxides of nitrogen and even ammonia, which Magnetite, or magnetic iron ore, Fe 3 4 , occurs in Sweden and
combines to form ammonium nitrate, may be formed.) North America.
Spathic iron ore, ironfU) carbonate, FeCO s , is found in Great
Action of alkalis on zinc Britain.
Iron is widely diffused and is present in many soils.
Zinc attacked by a hot concentrated caustic alkali solution.
is

(Zinc oxide is amphoteric, see p. 259.) Hydrogen is evolved and

Extraction
sodium or potassium zincate solution is left.
Since the demand for iron is so great (345 million tonnes of pig iron
Zn + 20H- + 2H gO -*- Zn(OH) t*~ + H, are made made from poorer grade ores,
yearly), iron has often to be
containing a certain amount of earthy impurities. The ores are first
Action of water on zinc
roasted in air when iron(lll) oxide, Fe t 3 is the main product.
,

Water does not attack zinc to any appreciable extent. Zinc at a red This ferric oxide is mixed with coke and limestone and introduced
into a blast furnace (Fig. 156). The blast furnace is a tall
heat is attacked by steam with the formation of hydrogen. structure

Zn +H 2
-> ZnO + H, about 30 m high and 9 m in diameter at the widest part. It contains

a firebrick lining inside a steel shell, and a blast of hot air can be
484 A NEW CERTIFICATE CHEMISTRY IRON 485

introduced low down through several pipes known as

in the furnace The above reaction liberates a very large quantity of heat, and it is
tuyeres. A well at the bottom of the furnace serves to hold the molten this heat which keeps up the high temperature necessary for the
iion and slag until these can be run off. The mixture of ore, coke and reduction process.
limestone is fed in continuously from the top, and a blast furnace, As the gas is forced higher up the furnace the supply of oxygen
(from the air) becomes less and the carbon dioxide coming into con-
tact with white-hot coke is reduced to carbon monoxide.
ferric oxide,
coke and limestone CO, + C -> 2CO
This carbon monoxide at the high temperature (about 1000°)
reduces the iron(HI) oxide to metallic iron forming carbon dioxide.
waste gases
to heat up Fe,O s + 3CO -*- 2Fe + 3CO,.
irorKIIQ carbon iron carbon
incoming air oxide monoxide dioxide

The molten iron runs to the bottom of the furnace.

Action of the limestone. The limestone, which has been introduced
together with the ore, is first decomposed at this high temperature to
form calcium oxide.
CaCOg »- CaO + CO,
calcium carbon
oxide dioxide

The earthy impurities contain a certain amount of silica (SiO,),

which an acidic oxide, and this combines with the basic oxide,
is

calcium oxide, to form calcium silicate.

SiO,
silica
+ CaO - CaSi0
calcium
3
silicate

tuyeres
(compare CO, + CaO -> CaCO s)

The form a molten slag

earthy impurities and this calcium silicate
which does not mix with the iron but floats above it and can be run
off separately. At one time this slag was a waste material, and the
slag countryside has been defaced by the presence of huge slag heaps. The
tapped here iron slag is being increasingly used at the present time for making roads.
tapped here The molten iron is run off into moulds, where it is allowed to cool
Fio. 156. in long bars about 1 m long and 10 cm in diameter. It is known as
The blast furnace. 'cast iron' or 'pig iron'.

Cast iron
once started, is kept going for months at a time until repairs are
necessary or work lacking. This is impure iron and contains varying amounts of impurities,
such as carbon (4%), with smaller quaiitities of silicon, phosphorus
Chemistry of the action and sulphur. This impure iron melts at a lower temperature than pure
iron and is brittle. It cannot be welded, and possesses little tensile
As the hot air comes into contact with the white-hot coke, the
strength. (Thus it could not be used for bridges or motor-car con-
latter burns to form carbon dioxide.
struction.) It is, however, used extensively for small castings, such as
C + O, -> CO, fire-grates, railings, hot-water pipes, Bunsen burner bases and for
carbon carbon
(col») dioxide
many other purposes where little strain is imposed.
486 A NEW CERTIFICATE CHEMISTRY IRON 487

Wrought iron Siemens process is to oxidise the impurities to their acidic oxides, and
This the purest form of iron, and is obtained from cast iron
is these combine with a basic lining supplied to the furnace. In this
by
heating with iron(III) oxide in a furnace by a process known
it process pig iron, scrap iron and iron oxide (the last of these supplies
as
'puddling'. The oxygen of the iron oxide oxidises the oxygen for oxidation of impurities) are melted in an open hearth
the impurities,
carbon and sulphur, to the gaseous oxides which escape, and which has been lined with a basic material (carbonates of calcium
phos-
phorus to phosphates and silicon to silicates, and these and magnesium are used, the oxides being formed at this high tem-
form as a
slag. The semi-molten mass is then hammered and rolled so that the perature). The amount of carbon is regulated at from 0.5% to 1%,
slag is squeezed out and a mass of almost pure iron remains. and small quantities of various metals such as manganese, nickel,
Wrought iron has a higher melting-point than cast iron. It is chromium or tungsten, are added according to the quality of the steel
malleable and can be forged, hammered and welded when hot. and the use to which the steel will be put
It is
Properties of steel. Steel is hard, tough and strong. If cooled
tough and fibrous, and can withstand some strain, but is not elastic,
and, if subjected to great strain, bend. gradually, steelcan subsequently be hammered into shape or drilled,
it will It cannot be tempered!
It is used to make
iron nails, sheeting, ornamental work, horse-shoes, because it is fairly soft By heating it and suddenly cooling it, the
steel becomes very hard indeed, of very high tensile strength,
and
and agricultural implements. It has been replaced to a large
extent regulated temperatures,
in recent years by mild steel, which can be made more cheaply. elastic. By reheating the steel to carefully

steels of different degrees of hardness and brittlenesscan be obtained.

Steel This is called 'tempering'.
Ordinary a material containing iron and a small proportion
steel is Uses of steel. Ordinary carbon steel, and alloy steels, have extensive
of carbon, the proportion being determined by the intended use
of and well-known uses, e.g., as armour plate in warships and military
the steel. About 90% of the pig iron made is converted into
steel.
tanks, as pressed sheet in automobile bodies, as girders and wire
Bessemer process. The usual Gilchrist-Thomas version of the mesh in ferroconcrete building, as cutting and boring tools, crushing
Bessemer process is as follows. The Bessemer converter is made of machinery and stainless cutlery. The following are a few examples:
steel plate lined with firebrick. It is roughly egg-shaped with armour plating, gears
an open with chromium (1-4%)
top and a base perforated to take an air-blast. It has a basic lining
with chromium (10-12%) stainless steel
of calcined dolomite (CaO and MgO). White-hot cast iron is run in in electromagnets
with cobalt (2-4%)
and an air-blast is applied. The various impurities of the cast iron drills and cutting tools.
with tungsten (5-18%)
oxidise— carbon to its gaseous oxides (CO and COj) which escape,
manganese and silicon to oxides which form a slag, and phosphorus
to its pentoxide, P 4 O 10 which is absorbed as a phosphate by the Physical properties of pure iron
,
basic
lining. When the appearance of the flame indicates the end State Solid.
of these
changes (about thirty minutes), the required content of carbon Appearance Pure iron is a white metal and can be
is
added to the metal as anthracite. A short air-blast is applied for polished.
mixing and the steel can then be poured. Density 7.9 g/cm- 3 .

Recently, the Linz-Donawitz (L-D) modification has been intro- Malleability Extremely malleable.
duced. The converter is similar but with a solid base. Instead Tensile strength High.
of an
air-blast from the base, an oxygen blast at 10 atm pressure is Melting-point 1535°C.
applied
over the top of the white-hot cast iron, by a water-cooled copper Conduction of heat
tube.
The rest of the process same and electricity Good.
is essentially the as before. Lime may be
added to assist formation of slag. Advantages of the L-D process are Iron can also be magnetised.
greater speed and a less brittle steel, because the oxygen blow con-
tains no nitrogen. Steel from this process is very suitable for pressing
Action of iron on exposure to air
motor-car bodies.
rusts, forming a
Siemens-Martin open hearth process. The chief impurities of cast In the presence of air and moisture, iron readily
oxide,
iron are non-metals, the oxides of which are acidic. The object of the reddish-brown solid which consists mainly of hydrated iron(IIl)
488 A NEW CERTIFICATE CHEMISTRY IRON 489

(Fe a 3 .xH aO). If finely divided (for example iron filings), it will burn bination; it is then said to act in the iron(II) (formerly called ferrous)
in air or oxygen to form the magnetic oxide of iron, Fe 3 4 .
state and produces the ion, Fea+ .

3Fe + 20 2 -»-Fe 3 4
If, however, the iron(II) ion is exposed to suitable oxidising con-
ditions, it will utilise a further electron for valency purposes.
The
Action of steam on heated iron resulting ion is then said to be in the iron(III) (formerly
called

Fe3
"
1".
Iron, at a red heat, is attacked by excess of steam, forming ferric) state as
magnetic oxide of iron (tri-iron tetroxide) and hydrogen. Fe2+ -* Fe3 * + er
3Fe + 4H aO -»• Fe 3 4 + 4H, The following table shows the formula (in molecular form) of the
tri-iron
more important simple compounds of iron.
tetroxide

The above action is reversible (see p. 158). IronOT) IronUll)

Valency of iron = 2 Valency of iron = 3
[Note that if air and water act together on iron, iron(III) oxide is formed, but
Ion Fe** Ion Fe>*
if cither of these substances acts separately the product is tri-iron tetroxide.]

Action of acids on iron Oxide FeO Fe 2 3

1. Dilute sulphuric and hydrochloric acids. Iron is attacked by these Hydroxide Fe(OH), Fe(OH) 3
dilute acids in accordance with the following equations: Chloride FeCU FeCl 3
Sulphate FeS0 4 Fe^SOJs
Fe + H S0 4 -»- FeS0 4 + H
2 2
Soluble iron(II) com- Soluble iron(III) com-
iron(II)
sulphate pounds give green sol- pounds give yellow or
Fe + 2HC1 -»• FeCI + H 2 2
utions. brown solutions.
ironfll)
chloride
Solutions of pure iron(II) compounds are distinguished from those
The iron(II) salt is obtained because the hydrogen which is given
of pure iron(III) compounds by the colour difference just mentioned,
off during the action is a reducing agent.
though, in dilute solution, the green colour of the iron(III) salts is
2. Nitric acid. Dilute nitric acid gives a series of complex reactions
very pale. Iron(III) hydroxide and iron(III) oxide are both brown,
in which oxides of nitrogen and even ammonia are formed.
while iron(ll) hydroxide, as usually precipitated, is green. IronfJI)
Passive state. If a piece of clean iron is dipped into concentrated
oxide is so readily oxidised by oxygen of the air that it cannot be kept
nitric acid there is apparently no action but the iron no longer
under ordinary laboratory conditions.
behaves as a piece of ordinary iron; for example, it will not displace
copper from copper sulphate solution nor is it attacked by dilute
A simple test for an iron{II) salt. Dissolve a little iron(II) sulphate
in water. To the solution, add sodium hydroxide (caustic soda) solu-
nitric acid, which normally does attack it. If, however, the piece of
iron scratched while in contact with, say, dilute nitric acid, a
is
tion. A
dirty-green, gelatinous precipitate of iron(II) hydroxide is
formed. This reaction is typical of a ferrous salt.
vigorous reaction occurs. This 'passive state' is supposed to be due
to a protective layer of oxide (Fe 3 4 ) formed on the iron by the Fe* + (aq) + 20H"(aq) -> Fe(OH) 2 (c)

strong oxidising agent, concentrated nitric acid. Where it is exposed to the the precipitate will become
air, brown
Iron will readily combine with sulphur and chlorine when heated because it is oxidised to iron(III) hydroxide.
with them to form iron(II) sulphide (p. 7) and iron(III) chloride 2Fe(OH) t + *0 2 + H gO ->- 2Fe(OH) 3
(p. 362) respectively.
A simple test for an iron(Ill) salt. Using iron(III) chloride solution,
Compounds of iron(I I ) and iron (ID) repeat the test just given. In this case, the precipitate is reddish brown
and is iron(III) hydroxide. This reaction is typical of an ironfJII) salt.
An iron atom possesses 26 electrons. The shell grouping normally
shown for them is 2, 8, 14, 2. The 2 adjacent to the 14 are the valency Fe3, (aq) + 30H"(aq) -* Fe(OH) 3(c)
electrons and the atom can part with them in electrovalent com- Conversion of an iron(ll) salt to an iron(lll) salt. The conversion of
490 A NEW CERTIFICATE CHEMISTRY LBAD 491

an iron(Il) salt to an iron(III) salt is an oxidation and is brought about The action of two common ones is represented in the following
by oxidising agents. equations.
Fe»+ — e- —* Fe 3+ + H S -*- 2FeCI, + 2HC1 + S
/2FeCl 3 2

To a solution of iron(II) sulphate, which is green, add dilute i or + S«- -> 2Fe* + + S
2Fe»+
sulphuric acid. Warm the mixture and add cautiously a few drops of Fe 2 (SO«) + S0 2 + 2H 2 -» 2FeS0 + 2H,S0
a
4 4

concentrated nitric acid. (A dark brown coloration will probably

appear. For an explanation of this see the 'brown ring' test, p. 436.)
C i or 2Fe 3+ + SO, + 2H O -> 2Fe» + S0 4 + 4H+
+
s
»-

Heat the mixture. Brown fumes of nitrogen dioxide are given off and
a brown or yellow solution remains. It contains iron(III) sulphate
LEAD
(test as described above). Occurrence
widely
The nitric acid has oxidised the iron(II) sulphate to iron(III) Lead occurs as galena, lead sulphide, PbS, and is distributed
being found to some extent in most parts of the
sulphate and has itself been reduced to nitrogen monoxide, which, in the earth's crust,
on exposure to gives nitrogen dioxide. has been known for a very long time— lead pipes were used
air, world. It

6FeS0 4 + 2HN0 3 + 3H S0 -+• SFe^SO,), + 4H + 2NO by the Romans in this country.

2 4 2
or 6Fe* ++ 8H + + 2NO - -»- 6Fe3+ + 4H + 2NO
s 2 Extraction
Iron(II) chloride converted by the oxidising agent, chlorine, to
roasted with excess of air to form lead(II) oxide.
is
The galena is
iron(lll) chloride, in solution or when heated.
2PbS + 30 a -»-2PbO + 2S0 2
2FeCI 3 + Cl 2 2FeCl 3
The oxide is then reduced to lead by heating with
carbon in a
or 2Fe 2+ + CI, 2Fes+ + 2CI-
small blast furnace.
Conversion of an iron(IU) salt to an iron(II) salt. The conversion of PbO + C->Pb + CO
an iron(III) salt to an iron(II) salt is a reduction, and is brought about
Some iron is added to reduce any remaining galena,
by reducing agents.
PbS + Fe-»-Pb + FeS
Fe» + + e--* Fe* +
and lime to combine with earthy impurities and
form a molten slag.
To
a solution of yellow iron(III) chloride, add hydrochloric acid
sulphide and slag are tapped off separately from
The molten iron(II)
and zinc. There is vigorous effervescence with evolution of hydrogen.
the lead.
Leave the mixture for 20 to 30 minutes. The colour of the liquid is
now green. It contains iron(II) chloride. (Test, after filtering, as New process for joint extraction of zinc and lead
described above.) and zinc
Substantial supplies of ores are known in which lead
The reduction here used to be ascribed to 'nascent' hydrogen, pro- new plant (in production in England in
A
sulphides occur together.
duced by the action of zinc and acid, used at the instant of its pro-
1968) extracts both metals in a single process.
duction and thought to be more active than ordinary gaseous
The ores (previously concentrated by flotation) are roasted in
hydrogen, which does not reduce an iron(III) salt in solution.
excess of air to form oxides.
2HC1+ Zn -> ZnCl, + 2H (nascent) 2ZnS + 30 2 -* 2ZnO + 2SO, (PbS similar)
2FeCl 3 + 2H -* 2FeCl, + 2HC1 into a blast
The oxides are dropped, with coke (reducing agent),
The modern (and better) explanation is that, in the presence of the furnace (p. 484) and are reduced to the corresponding
metals.
acid, zinc supplies electrons which are taken up by the iron(III) C -»• Pb CO
which are thereby reduced to iron(II) ions.
ions,
ZnO + C-*Zn +
CO; PbO + +
Molten lead settles to the base of the furnace, with some slag, and is
tapped off periodically. Zinc is vaporised and leaves the furnace by
of carbon.
a pipe near the top, together with nitrogen and oxides
lead. The
Other reducing agents will convert iron(III) salts to iron(II) salts. Zinc vapour is stripped from the gases by a spray of molten
 COPPER 493
492 A NBW CBRTIFICATB CHBMISTRY
mixture of zinc and lead flows into shallow tanks where molten If lead is strongly heated in air it forms litharge (a yellow powder)
zinc separates above the much denser molten lead and can be tapped
which is a form of lead(II) oxide
off separately. The lead is returned to the stripping circuit The 2Pb + OJ-+ 2PbO
process is continuous and economical in both manpower and heating but if heated to a carefully regulated temperature of about 450°C red
costs; a disadvantage is that 400 tonnes of molten lead must be formed.
pumped round per tonne of zinc extracted.
lead is

3Pb + 20 a
- Pb 3 4
(red lead)
Isotopes of lead

Lead a product of radioactive change. As such, Action of acids on lead

is it is found in

association with natural deposits of uranium and thorium, both of Dilute sulphuric acid and dilute hydrochloric acid have no action
which are radioactive. Uranium (U = 238) is converted to lead by on lead.
the loss of eight alpha-particles, each of mass 4, from its nucleus. Hot concentrated sulphuric acid attacks lead (compare copper):
This gives a lead isotope, Pb = 206. Thorium (Th =
232) loses six
alpha-particles per atom and gives a lead isotope, Pb = 208. Ex-
Pb + 2H t S0 4 -
PbS0 4 + 2H aO + SO a
lead(II) sulphur
perimental tests have shown the correctness of these two atomic sulphate dioxide

weights for samples of lead extracted from uranium and thorium Nitric acid attacks it forming nitrogen monoxide (chiefly).
minerals. The heavier isotope has two additional neutrons on the
atomic nucleus, but both isotopes have the same number of nuclear
3Pb + 8HNO
dilute nitric
s
- 3Pb(N0
lead(II)
3) 2 + 4H O + 2NO
water
s
nitrogen
protons (82) and the same electron arrangement, so they are chem- acid nitrate monoxide
ically identical. Ordinary lead is an isotopic mixture, Pb =
207.2. The only satisfactory laboratory method of obtaining
lead in solution is by the action of dilute nitric acid to form
Physical properties of lead lead nitrate solution.
State Solid.
Appearance Bluish white.
Uses of lead
Density 11.3g/cm-».
(1) Lead is used extensively in the manufacture of water and gas
Malleability Very malleable. Can be cut with a knife.
piping and as lead sheet for roofing. It is particularly valuable for
Has a metallic lustre but speedily
piping as it is easily repaired and joints are quickly made. It is also
tarnishes.
Tensile strength soft and bends easily at corners. It is also used in the manufacture of
Fair.
lead shot, solder, pewter and type-metal.
Melting-point 327°C
Conduction of heat (2) For paint. If lead is exposed to the action of acetic acid, air,

and electricity. Good conductor of heat and
electricity.
Action of air and water on lead
Lead is attacked by air and water together, a white layer being
formed on the lead which consists of a mixture of lead hydroxide and
lead carbonate. Lead is used extensively as piping to carry water
supplies and cases of poisoning have been traced to the removal of
this layer of hydroxide and carbonate by the water passing through.
If the water is slightly 'hard' (see p. 201) a protective coat appears to
be formed and none of the lead is removed. In many water supplies
nowadays, the water is specially hardened by the addition of lime to
prevent any of these poisonous effects.
water-vapour and carbon dioxide, it is converted into a basic car-
bonate known as white lead (Pb(OH) s .2PbCO a ) and as such is used
for paint.
(3) Lead is used in the manufacture of electrical accumulators and
as a covering material for cables.
COPPER
Occurrence
Native copper or boulder copper is found as the element round the
shores of Lake Superior but most of the copper used in industry
occurs as copper pyrites, CuFeS a.
494 A NEW CERTIFICATE CHEMISTRY MAGNESIUM 495

Extraction from boulder copper Action of air and water on copper

This ismerely refined, very often on the spot, by building a con- Copper is air or water, but, when exposed to
not attacked by pure
tainer round the copper, filling the container with copper(II) the atmosphere, slowly attacked on the surface with the forma-
it is

sulphate solution and making the impure native copper the anode of tion of a green solid. This is probably a basic sulphate.
a cell (Fig. 157). A strip of copper is made the cathode and pure When heated in the air, copper forms a layer of black copperfU)
oxide on the surface.
-Pole Pure
ire Copper
Co,
deposit here
2Cu + 2
-»• 2CuO
Action of acids on copper
Copper has no action on either dilute sulphuric acid or dilute
hydrochloric acid.
With dilute nitric acid, oxides of nitrogen are liberated, chiefly
Boulder Copper nitrogen monoxide, and a blue or bluish-green solution of copper(II)
Impure
nitrate remains.

3Cu + 8HN0 3
-»- 3Cu(N0 3) 2 + 4H 2 + 2NO
dilute nitric copper(II) water nitrogen
acid nitrate monoxide
.Copper Sulphate
solution With hot concentrated sulphuric acid sulphur dioxide is liberated
and copper(II) sulphate is formed.
Cu + 2H S0 4 -»- CuS0 +
2 4
2H 2 + SO a
Fio. 157.
Purification of boulder copper where (he metal is found. Flame coloration
Copper salts colour the flame a characteristic bluish green.
copper deposits on this from the anode as the electrolysis proceeds.
(See electrolysis of copper sulphate solution, p. 149). Uses of copper
At cathode At anode 1. For conducting electric current. It must be very pure because im-
Cu a+ + 2e~ —> Cuj. Cu — 2e~ -»- Cu*+ purities increase electrical resistance.
2. For ornamental work, being little attacked by the air.
Extraction of copper from copper pyrites 3.In alloys, e.g., brass (Cu and Zn), bronze (Cu and Sn), German silver
(Cu, Zn and Ni) and the copper coinage (Cu and Sn).
The extraction from sulphur-containing ores is long and tedious
since the copper must be of a high degree of purity, otherwise it is MAGNESIUM
useless for electrical purposes. The chemistry of the process is too Magnesium extracted by electrolysis of fused magnesium chloride.
is
difficult for inclusion here.
This salt is now prepared from sea-water which contains about 1 million
tonnes of Mg ,+ per km*. Sodium chloride (see diagram) reduces the
Physical properties of copper melting-point of magnesium chloride and allows a lower working tempera-
State Solid. ture. Molten magnesium collects and is protected from oxidation by a coat-
ing of electrolyte and from anodic chlorine by the porcelain sheath.
Appearance A red metal possessing a lustre. It can be At cathode Mg»+ + 2e~ —> Mg; at anode 2C1" - 2e~ —> CI,.
polished.
Density 8.95 g/cm-8 . Properties of magnesium
Malleability Very malleable and ductile. Magnesium bums readily when heated in air to produce magnesium
Tensile strength The metal is of fairly high tensile strength. oxide and nitride.
Melting-point 1080°C. 2Mg + O, —* 2MgO ; 3Mg + N, -»• Mg 3 Nj
Conduction of heat It isan excellent conductor of both heat It reacts slowly with boiling water to liberate hydrogen
and electricity and electricity. Mg + 2H.O -* Mg(OH), + H,
496 A NEW CERTIFICATE CHEMISTRY QUESTIONS 497

and burns rapidly when heated in steam (p. 197). All the dilute mineral
acids react with magnesium at room temperature. Hydrochloric and sul-
QUESTIONS
phuric acids liberate hydrogen. 1. What are the chief chemical properties which distinguish the metals
Mg + 2H+—>-Mg*+ + H, from the non-metallic elements?
When very dilute, nitric acid may liberate some hydrogen but, with ordinary Give three distinct methods by which metals can be converted into their
oxides, using iron, copper and zinc as examples,
and state how the oxides
dilute acid, a complex reaction occurs with oxides of nitrogen liberated.
These reactions show the strongly electropositive nature of magnesium. of these metals may be distinguished from one another. (B.)
2 Illustrate, by reference to two chemical and to four physical proper-
Cordon anode ties the chief differences between the
metals and the non-metals. Describe
briefly how a metal may be isolated from (a) a
naturally occurring sulphide,
and (b) a naturally occurring carbonate. (N.U.J.B.)
Iron cathode
3 Give the chemistry of the extraction of iron from hsmatite (ironflXf)
_ (and
would you prepare (a) iron(llJ) oxide starting from iron(lll)
— container) oxide). How
chloride; (b) anhydrous iron(II) chloride starting from iron? (N.U.J.B.)
Magnesium 4. Name the products, if any, formed when

(a) air is passed over heated (i) iron; (ii) copper; (in) carbon.
'orce/ain
sheath (b) steam is passed over heated (f) iron; (ii) copper; (ui) carbon.
fused riaqnesium (c) hydrogen is passed over heated (i) black iron oxide; (ii) copper
Chloride (with oxide.
Sodium Chloride) Give the equations for
(a") of these reactions which shows simultaneous oxidation and
one
Fio. 158. reduction.
Extraction of magnesium. («) two of these reactions which
together illustrate one reversible

Uses of magnesium change. (N.U.J.B.)

1. In several light alloys. For these, see aluminium, p. 479.
2. As powder, with an oxidising agent such as potassium chlorate, in
flares and fireworks.
Electroplating
Electroplating is the electrical precipitation of one metal on another to
secure improved appearance or greater resistance to corrosion.
In silver plating, articles such as table-ware or cake dishes, made of
base alloy, e.g., cupronickcl, are made the cathode in a plating bath of
potassium (or sodium) argentocyanide, KAg(CN)„ solution. This contains
5. Explain what is meant by the statement that iron forms two series of
salts.Describe how you would prepare from metallic iron one member of
each of these series, and give one physical and one chemical distinguishing
test for (a) iron(ll); (/>) iron(III) salts. (B.)
6. Outline the chemistry of the extraction of (a)
zinc from zinc carbonate
(calamine); (a) lead from lead sulphide (galena).
State two general methods of preparing salts, and illustrate each method
by reference to the preparation of a zinc salt. (N.U.J.B.)
chemistry of the
7. The chief ore of zinc is zinc blende, ZnS. Outline the

some silver ion, Ag+. extraction of zinc from this ore. State two important uses of zinc. Starting
from zinc, how would you prepare specimens of (a) zinc oxide and (b)
KAg(CN), ^ K+ + Ag+ + 2CN- crystalline zinc sulphate? (N.U.J.B.)
The anode is pure silver. When direct current passes, the following occurs. Describe the electrolytic process for the refining of copper. Name four
8.
At cathode Ag + + e~ —
Ag At anode Ag — e~ —* Ag+ distinct usesof copper. .

Silver deposits Silver dissolves
In correct conditions, the silver layer deposited on the cathode article is
coherent and tough and can be highly polished.
Chromium plating is much used to improve the appearance of steel
parts and protect them from rusting. The steel is usually plated first with
nickel or copper, because chromium does not adhere well on to a steel
surface. The object is made the cathode in a plating bath which contains
chromium compounds (e.g., sulphate and oxide) in sulphuric acid and
water. A lead anode is usual. When direct current passes, chromium
deposits on the article at the cathode as a bright coherent layer.
Cr*+ + 3e--*-Cr
This layer resists rusting and gives a bright 'silvery' appearance.
Starting with cupric oxide, how would you obtain (a) a dry crystalline
specimen of copper(ID sulphate; (6) a sample of metallic copper?
9. Select, from the following, the decisive
reason for regarding (a) zinc
as a metal, (6) bromine as a non-metal (a) (i) zinc is
:
much denser than
water, (ii) zinc conducts electricity well, (iii) zinc is an
electropositive
element, (iv) zinc is malleable at certain temperatures; (b) (i) bromine is a
liquid at s.t.p., (ii) bromine is an electronegative element, (iii) bromine is
much less dense than mercury, (iv) bromine combines fairly readily with
hydrogen.
 radioactivity; a brief account 499

particles of which beta-rays are composed carry a negative charge and

are relatively small in mass. Beta-rays have since been shown to con-
sist of electrons in rapid motion. Beta-radiation is simply a moving
stream of electrons.
Chapter 37 Gamma-rays were not deflected at all by an electrostatic field; that
is, gamma-rays carry no electrical charge. They are not material

particles but consist of electromagnetic waves of very short wave-

-
length (about 5 X 10 " cm). That is, they are of the same nature as
Radioactivity; a Brief Account light but of higher frequency.

Selecting
Particle of screens Electrostatic field
noticed and investigated by Beta-rays^
RADIOACTIVITY was first in 1896 uranium salt 1/ ^M
Becquerel, taking place in salts of uranium. Becquerel found that iamma-raya
these salts emitted rays with the following properties. They affected
a photographic plate in the same way as rays of light, discharged a
gold-leaf electroscope and caused phosphorescence in certain
B Fig. 159.
Alpha-rays

materials, e.g., zinc sulphide. Becquerel did not follow this investiga- Composite radiation from uranium salt.

tion very far, but his discoveries aroused interest and activity in other
workers. In particular, Marie and Pierre Curie, working in Paris Nature of radioactivity
about 1900, detected more intense radioactivity in certain mineral
Itwas soon noticed that radioactivity is very different from ordinary
specimens, such as Bohemian pitchblende, and were able to isolate
chemical change. It is, for example, unaffected by temperature
two radioactive elements, to which they gave the names polonium (in
changes of the kind occurring in common scientific operations, being
honour of Marie Curie's native Poland) and radium. Many other —
as rapid at the temperature of liquid air (about 180°C) as at red
radioactive elements are now known.
heat (about 850°C), while chemical change is usually greatly acceler-
Kinds of radiation ated by marked rise of temperature.
After a period of general uncertainty, Rutherford and Soddy put
Becquerel found that the radiation emitted by uranium was not
forward the idea, now universally accepted, that radioactivity arises
uniform but could be separated into three different types under the
from the spontaneous disintegration of unstable atomic nuclei. In
influence of an electrostatic field. The three types were named alpha-,
fact, all atomic nuclei more complex than the nucleus of the bismuth
beta- and gamma-rays.
atom (that is, containing more than 83 protons) are unstable. By
Alpha-rays were deflected towards the negative plate in the electro-
disintegration, all such complex nuclei give rise to radioactivity. For
static field and so, since unlike charges attact each other, must carry
example, the polonium atomic nucleus has 84 protons, the radium
a positive charge themselves. The deflection was not very marked,
nucleus has 88 protons and the uranium nucleus 92 protons. To take
from which it was concluded that the moving particles constituting
a particular example, the radioactivity of radium is caused by the
the rays were relatively massive. It has since been shown that alpha- 8+
emission of an alpha-particle (helium ion, He ) from the nucleus of
rays are, in fact, helium ions in rapid motion. Helium ions are formed
a radium atom. The helium ion carries away with it two protons (as
from helium atoms by loss of two electrons per atom. They then
well as two neutrons). This leaves behind an atomic nucleus contain-
carry a double positive charge resulting from their possession of two
ing 86 protons and this is the nucleus of an atom of the rare gas,
nuclear protons and have a mass of about 4 units on the scale of
radon. This change is accompanied by a very large evolution of
"C = 12. 8
energy (about 4 x 10 kJ per mole of radium) so that a solution of
He -»• He* + + 2e~
a radium salt maintains itself at a temperature above that of its sur-
Beta-rays showed a very marked deflection towards the positive roundings. This radioactive change can be expressed by the equation:
plate of the electrostatic field. From this, it was concluded that the
498
500 A NEW CERTIFICATE CHEMISTRY
In chemical symbols of this kind, the lower figures are the atomic
numbers of the elements concerned, e.g., atomic number of radium
is 88, and this is the number of protons on the nucleus of this atom.
The upper figures are the mass numbers of the elements concerned,
e.g., the mass number of radon is 222. This is the total number of
protons and neutrons present in the atomic nucleus of radon. From
this it follows that the difference between the mass number and the
atomic number of an element is the number of neutrons in the nucleus
of its atom. The symbol, Z is used for atomic number and the symbol,
A, for the mass number of an element, so that:
Number of neutrons in the nucleus = (A — Z)
For example, the nucleus of the radium atom contains (226 — 88),
or 138 neutrons.
Equations of the above kind must balance by having equal totals of
atomic numbers and of mass numbers on each side. For the mass
numbers, 226 on the left is balanced by (222 +
4) on the right; for
the atomic numbers, 88 on the left is balanced by (86 + 2) on the
right. In a similar way, the following equation expresses the fact that
a sulphur atom can absorb a neutron and then emit a proton, so
producing an atom of phosphorus.
Both the proton and the neutron have a mass of approximately 1 on
thescaleof'*C = 12. This accounts for the upper figures. The neutron
has no charge, therefore has atomic number 0; the proton, with its
single positive charge,has atomic number I. This accounts for the
lower figures and the equation balances as required.
Results of radioactive changes
Ithas been found that there are two important kinds of radioactive
change.
(1) Emission of alpha-particle. In this case, an atomic nucleus
emits an alpha-particle, that is, a helium ion containing two protons
and two neutrons. In this way the nucleus loses 4 units of mass. The
two lost protons reduce the atomic numberof the element by two units,
consequently the product of the change is an atom with a mass
number reduced by 4 units and an atomic number reduced by two
units in comparison with the original atom. An example of this is
'55Ra- s ";
2
«Rn He
(alpha-
particle)
(2) Emission of beta-particle (or electron). This kind of radioactive
change is equivalent to the splitting of a neutron in the atomic nucleus
of the radioactive element into an electron and a proton, the proton
radioactivity; a brief account 501
being then retained by the nucleus while the electron is emitted as
beta-radiation. The electron is a very light particle and its loss makes
no significant change in the atomic mass of the atom concerned. The
retention of the proton raises the atomic number of the element by
one unit. That is, the product has the same mass number as the
original atom and an atomic number one unit greater. For example,
a radioactive isotope of lead can lose a beta-particle to produce an
atom of bismuth.
2
>2Pb-*nSBi + .?e
In terms of atomic number, a beta-particle (electron) being negatively
charged counts as (—1), just as a proton positively charged counts
as(+l).
These types of change continue till a stable atomic nucleus is
reached. It is now recognised that there are several series of radio-
active change, named after the elements from which they originate in
nature, e.g., the uranium series, the thorium series and the actinium
series. The changes can be very complex. In the uranium series, the
original uranium atom passes through radium as an intermediate
an atom of non-radioactive lead.
and finishes as
2381] 2 I pu
rU
s^Ra (1
8S
The uranium atom loses 10 protons in all, reducing its atomic number
by ten units. It also loses 32 units of atomic mass.
These changes occur in pitchblende, a uranium ore from Bohemia,
and the source of the radium isolated by the Curie's. The ore also
contains helium gas occluded in it. This gas is derived from the alpha-
particles (helium ions) emitted during the radioactive changes.
Stability of radioactive elements
The mathematics of radioactive change is rather complex, but it
leads to the conclusion that a convenient way of expressing the degree
of stability of a radioactive element is to state its half-life, that is the
time required for its radioactivity to fall to half its observed valueat
any given instant. A half-life may vary from a fraction of a second for
very unstable elements to millions of years. Radium has a half-life
of 1620 years; that is, any mass of radium existing in 1900 will have
diminished to half that mass by about the year 3520.
Artificial nuclear transmutation
From what has been written above, it is obvious that radioactivity
transforms the radioactive element into a different clement. This
change is called transmutation of elements. The early radioactive
changes observed were all spontaneous and uncontrollable, but efforts
were soon made to bring about artificial transmutations by experi-
mental means. The first success was that of Rutherford (1919) who
502 A NEW CERTIFICATE CHEMISTRY radioactivity; a brief account 503
transmuted nitrogen into oxygen. The nitrogen was subjected to the By the Einstein equation quoted above, this loss of mass (in grams)
action of swift alpha-particles, derived from a radium salt. The corresponds to the radiation of 21 X 10 9 kJ of energy. The actual
nucleus of a nitrogen atom captured one of these alpha-particles and fission is much more complex than this but the principle is not
then emitted a proton, leaving an oxygen atom as the product. affected.
»fN + !He->- 'JO+ \p This process of nuclear fission made into a chain
of U-235 can be
Many other transmutations have since been achieved. Some of them reaction in suitable conditions. This because, while fission occurs
is

are mentioned later when radioactive isotopes are considered. as a result of neutron absorption by the uranium nucleus, the process
of fission also emits neutrons. These are available for absorption to
Nuclear energy produce new fissions, and so on. If the mass of uranium is small, the
has already been noticed that radioactive changes can be accom-
It neutrons may escape from it at such a rate that the chain reaction
panied by very great evolutions of energy in the form of heat, e.g., cannot be maintained, but, above a certain critical mass, the uranium
s
!|Ra->- 2
!iSRn+ JHe; A# = -(4 X 10s ) kJ. absorbs the neutrons so as to produce very rapid nuclear fission of at
It was soon realised that if arrangements could be made to isolate
Neutron id
radioactive materials and then control their activity, a new and very produce other
fissions Radiation of
important source of energy would be made available for the human \

y
energy
race. Unfortunately the first supplies of energy from this source were
used for destructive purposes in two atomic bombs at the close of the Nucleus of an Nucieus of an
atom of atom of 236
World War of 1939-45. This development depended on the following
circumstances.
In 1939, the German nuclear scientist, Hahn, discovered that the Neutron to produce
atomic nucleus of the isotope of uranium, '"U, could absorb a other fissons
o-
*
neutron and then break into two roughly equal parts. This is called
atomic fission. The total products of the fission have a mass slightly
Neutron absorbed
less than that of the total initial material. This difference of mass is by nucleus of 235 1

radiated as energy, the amount of energy being slated by the equation 32 U Two smaller nuclei of
atomic number near to 46
of Einstein,
E=mc* Fio. 160.
Fission of U-235.
where E is the liberated energy in ergs
m is the mass in grams least a substantial proportion of it. The energy liberated then pro-
c is the velocity of light in cm/sec (c =3 X 108 )
duces a terrific explosion, with a temperature of several million degrees
The factor, c, is so large, especially when squared, that the loss of a centigrade immediately after its occurrence.
small quantity of mass brings the liberation of an enormous quantity The essential ideas relating to the production of the first atomic
of energy. In a typical fission, the U-235 may be considered to absorb bomb were the following.
one neutron per atom, and then to undergo fission to produce one (1) A sufficient amount of U-235 had to be isolated from a natural
atom each of molybdenum and lanthanum, together with two source of uranium, which contains about 0.7% of U-235 and 99.3%
neutrons. The accurate masses involved will then be: of another isotope, U-238. (Both isotopes have atomic number 92.)
The separation of the isotopes was brought about by producing the
Before fission After fission
fluorides,UF„ which are gaseous. U-238 produces a fluoride of
Uranium atom 235.125 Molybdenum atom 94.945
higher molecular weight than U-235. The U-235 fluoride conse-
Neutron 1.009 Lanthanum atom 138.955
quently diffuses more rapidly than the U-238 fluoride (Graham's
Total 236.134 Two neutrons 2.018
Law). The two fluorides were separated in the U.S.A. by very elaborate
Total 235.918
apparatus for fractional diffusion, and then the U-235 was obtained
Loss of mass during fission = (236.134 - 235.918) = 0.216 pure by decomposing the fluoride into its elements by heat. ,
 ^
504 A NEW CERTIFICATE CHEMISTRY RADIOACTIVITY; A BRIEF ACCOUNT 505

(2) A mechanism was constructed to keep the U-235 apart in scale of 12

C=
12. The lost mass is radiated as energy in accordance

quantities below the critical mass until the decisive moment and then with Einstein's equation mentioned earlier, E =
mc 2. The conversion
shoot them rapidly together to form one unit greater than the critical of hydrogen to helium does not take place directly. A scheme has
mass. A
source of neutrons was also required to initiate the fission. been suggested by which carbon intervenes in the process as 'catalyst',
(3) A
tamping device in the form of suitably shaped, thick steel in a series of nuclear changes which also involve '73 N, \s O and other

sheet was placed round the uraniumto reflect escaping neutrons back
2 B
into the fissionable material. The
isotope of plutonium, l ,P\i, will
also undergo nuclear fission and produce a similar chain reaction. It
was also used in an atomic bomb in 1945.
The problem of adapting fission processes for useful purposes is
that of releasing thesame energy as in the fission bombs, but steadily
over a relatively long period and at a temperature convenient for
making use of the energy. The British Calder Hall reactor (1956) was
based upon experience with an experimental atomic pile at Harwell.
To avoid the very expensive separation of U-235, natural uranium
was employed. By the use of pure graphite, fast neutrons were
slowed to a velocity such that they are not absorbed by the U-238
present, but are available for the U-235 fission. This occurs rapidly
enough to maintain the chain reaction. Energy is released steadily as
heat, which can be absorbed by a circulating gas and applied for the
production of power. At Calder Hall, carbon dioxide at about 7 atm
pressure is used and the gas leaves the reactor at about 350°C. The
heal is conveyed to boilers and used to produce steam, which in turn
generates electrical power through alternators.
In the experimental pile at Harwell, about 40 tonnes of uranium, in
long bars of 6 cm 2 cross-section, were distributed regularly about
isotopes, to bring about the net change of hydrogen to helium.
Temperatures of the order of millions of degrees centigrade are
necessary and, even then, the conversion of hydrogen to helium is
slow. The sun is estimated to contain enough hydrogen to continue
radiating at its present rate for, at any rate, several thousand million
years. A process of this kind in which several atoms produce a more
complex atom is called atomic fusion.
The hydrogen bomb uses an adaptation of the synthesis of helium
from hydrogen, which occurs in the sun. In one version of this bomb,
the two heavier isotopes of hydrogen, deuterium, jD, and tritium, JT,
are fused to produce helium and neutrons.
;D + fT-*JHe+ In
During about 0.4% of the original mass is converted to
this process,
energy. So great is this release of energy that an approximate tonne
of material used in the hydrogen bomb is as destructive as several
million tonnes of ordinary military explosive such as TNT. Deuterium
can be obtained from water. Tritium is a product of the action of slow
neutrons on lithium.
|Li + Jn-*?T+ J He
The temperature required for their fusion is several million degrees

17 apart both ways in 800 tonnes of pure graphite blocks. The

cm
metal was sheathed in aluminium to protect uranium from oxida-
tion and to hold the fission products together. There was an arrange-
ment of control rods which could be wound into the pile, if danger
threatened, to absorb neutrons and prevent the pile from going
out of control. The rods contained boron. For safety, the pile was
surrounded by an adequate thickness of concrete to absorb stray
radiation.
Sources of stellar energy
Development of knowledge about atomic energy has revived
interest in the sources of energy in the stars, especially the sun.
centigrade and is supplied by the action of a uranium fission bomb
round which the fusion materials are placed.
Artificial elements
The most complex atomic nucleus known on the earth up to about
1940 was that of uranium (atomic number 92). Recently, more com-
plex nuclei have been assembled. The first two of these can be pro-
duced by exposing U-238 to neutron bombardment. U-238 captures
a neutron to give the isotope, U-239. This passes, by a stage of beta-
decay, into neptunium and then, by a similar stage, into plutonium.
These elements have atomic numbers of 93 and 94 respectively and
A were previously unknown. Both are radioactive and plutonium is

recent suggestion is that the output of energy in the sun may be fissionable.

maintained by the conversion of hydrogen into helium. By this *i!U + 230IJ

process, four hydrogen nuclei (protons) are converted to one helium

338
INp + .f*
nucleus (alpha-particle) with the liberation of very large amounts of JSNp-
energy. This energy appears because the helium atom (4.0026) has a Other, more complex, nuclei have also been produced in recent years
mass slightly less than that of four hydrogen atoms (4.0319) on the to atomic number 103 (Lawrencium, Lw), though some of them have
506 A NEW CERTIFICATE CHEMISTRY radioactivity; A BRIEF ACCOUNT 507

occurred in very minute amounts, such as a few hundred atoms, and Radium was formerly used for this purpose but radio-cobalt has
some are very unstable. taken its place. This material is made by irradiating ordinary cobalt,
It will be seen from the above account that the alchemists' dream of 5? Co, with neutrons.
converting one element into another has now become a common- »?Co+»n-»-S?Co
place of physics. Their idea of converting base metal into gold is, The product, is radioactive, emitting very penetrative
cobalt-60,
however, somewhat beside the point To do this would either liberate gamma-rays. placed at the centre of a sphere of lead which sup-
It is

or absorb great quantities of energy, depending on the nature of the presses most of the radiation, which would be dangerous to operators.
base metal used. In the first case, the value of the energy would dwarf A narrow radial boring in the sphere allows a pencil of the radiation
that of the gold; in the second case, the cost of the gold in energy to escape and it is directed at the diseased tissue. Radioactive phos-
would be prohibitive. phorus, J^P, has been tried in compounds for treatment of leukaemia,
and radio-iodine for treating thyroid disease.
Radioactive isotopes of common elements
Radio-strontium, or strontium-90, SJjJSr, also emits destructive-
Radioactivity was discovered in the most complex atoms, such as radiation. (Ordinary strontium is mainly JjfSr and is not radioactive.)

those of uranium, polonium and radium, and, in nature, is restricted Strontium-90 contained in the fall-out from certain kinds of atomic
is

mainly to atoms of this kind. It is possible, however, by methods
outlined below, to produce radioactive isotopes of many common
elements and to employ them usefully in various ways. Such radio-
active isotopes usually have a short half-life (a few days or weeks) and
so decay to vanishing point quite rapidly. This is why they are not
found in nature to any noticeable extent.
Two examples of the production of radioactive isotopes of common
elements are the following.
(1) If a sodium salt, such as the chloride or carbonate, is irradiated
by an intense concentration of neutrons in a uranium pile for a few
days, some of the sodium atoms (mass number 23) will absorb a
neutron each to give radio-sodium atoms (mass number 24), which
are radioactive.
??Na+Jn-»-?}Na
(2) In conditions similar to the above, sulphur atoms will
one neutron each, then radiate a proton and finish as a radioactive
bomb tests. If it is absorbed into bone tissue in man above a certain
concentration, its radiation may set up a severe, possibly fatal, disease
of the blood by destroying bone-marrow and red blood corpuscles.
This is one of the objections to the testing of such bombs in quantity.
(2) Uses in scientific research. These uses are mainly examples of
tracer technique. Living organisms do not distinguish between
ordinary atoms and their radioactive isotopes. A radioactive form of
an clement can, therefore, be used, highly diluted, as a marker to
trace, by its radioactivity, what happens to this element during the
growth of the organism. A notable example of this technique has
been the use (by Calvin in the U.S.A.) of radio-carbon, V
C, as carbon
dioxide, to trace the course of photosynthesis in plants. Many other
similar cases have been reported and the method is increasingly used.
absorb

form of phosphorus.
SSS+jji-KilP+l*
Ordinary phosphorus is J J P.

Uses of radioactive isotopes

These uses are principally curative, general industrial uses and uses
in scientific research.
(1)Curative uses. Cancerous growths may sometimes be eradicated
by exposure to gamma-rays (i.e., electromagnetic waves of very high
frequency), which are derived from radioactive materials. Both 5 10 15 20 25 30
healthy and diseased tissue are destroyed by uncontrolled exposure, Time in thousands ofyears •

but by regulating the dosage and directing it suitably, healthy tissue

Fig. 161.
can be protected. Rate of decay of radioactivity in radio-carbon.
508 A NEW CERTIFICATE CHEMISTRY
Radio-carbon also plays a part in the dating of archaeological
specimens. This form of carbon occurs in the carbon dioxide of the
atmosphere in a constant proportion. It is taken into the tissue of
growing trees in this proportion. When the umber is cut, the radio-
of the radio-carbon decays at a known rate (half-life of radio-
activity
carbon is 5760 years). Consequently, if the present, reduced radio-
Chapter 38
activity of an ancient sample of wood is determined, the age of the
wood can be estimated. Such estimates agree closely with datings
from other (historical) evidence where it is available, so can be used Revision Notes
for dating fresh specimens of ancient tools, domestic articles and
weapons.
(3) Industrial uses. These uses of radioactivity are many and in-
creasing. Radio-sodium,
detection of leaks in
employed as carbonate, is used for rapid
water-mains. The point of leakage can be found
NO two students will revise in quite the
revision concentration is essential,
same way. For proper
and the following method is
suggested, because it does ensure concentration.
by the of radio-sodium on a Geiger counter. Similarly, when
effect
the grade of oil is changed in a pipe-line, radioactive material can be
(a) Self-expression
added at the change-point and is easily detected at the receiving end.
Other uses of radioactive materials are in the inspection of welded Suppose you are revising a topic such as 'Chlorine and Chlorides'.
steam-pipes and boiler-plates for the detection of faults; and for the It does not matter what the subject is, the procedure is the same.

dissipation of electrostatic charges built up by friction on moving
bands. Such charges can cause sparking, which is dangerous in certain
environments.
Begin with a pencil and a large sheet of paper. Write down in note
form as many important ways of making chlorine as you can. Write
down briefly its properties, under headings if such classification is
possible. Make a list of all the metallic chlorides you know, show
how to prepare them, and state their principal properties. For the
preparation of many substances a well-labelled diagram, apart from
the equation, will be all that is required for this purpose. Draw the
diagram freehand, or use a stencil, for all that is required of a diagram
is to show clearly the apparatus you would use. This need not be an

'art* as well as a chemistry exercise.

Write down all you can, and do not give in too quickly, for there is
a very great difference between a hasty revision and one in which you
are determined to give in only when you have put down all the points
you can possibly remember. Now turn to your book and you will
find the correct answer to many points about which you were doubt-
ful, and many points you did not know at all! The next time you
revise that chapter, which should be some time after the first revision,
you may content yourself with writing down only those points which
you did not know before. The thing to remember is that true revision
must involve self-expression. The following revision exercises are
arranged with that point in mind.

(b) Approach the subject from a different angle

If you have followed the book, you will have met most
text of this
of the matter about the various salts classified according to the acid
509
510 A NEW CERTIFICATE CHEMISTRY
radical contained in them. Thus all metallic carbonates are discussed
under 'carbonates', because they are similar in many ways, and all — - 1 1 1 1 1

metal oxides are discussed under 'oxides' and so on.

Now attempt to revise in a different way by picking out one metal, 1

--
for example copper, and writing down the preparation and properties o CS .—1 1 1 1 O 1

S:
of its various compounds. Because this may waste a lot of time over
unimportant compounds and because a little help often goes a long
way, the table on p. 511 has been drawn up to give you the starting - ro c> - 1 1 1

point for a revision of this type. i

To use this table for any particular metal, for example, copper:
^* ^-i 1 1 1

Write down on a sheet of paper the formula for coppcr(II) oxide,

1 1

hydroxide, chloride, sulphate, nitrate, carbonate, sulphide. i

Give a few words and properties,

to indicate their preparation d
en
- - 1 1 1 1 1

including such actions as those of heat, water, acids, alkalis, con- X

centrated sulphuric acid, etc. By omitting certain numbers you can
make the revision just as superficial or thorough as you please.
!>.
~H •-H 1 1
•-« CS CS o — ^*
o
By way you approach a
revising in this the matter from an
i
M
and you test your capacity to extract
entirely different angle
CS o c» ~* — 1
»-* CI -* 1 HJ — o
c c
any required knowledge from its context. 8 3 ^
i
f
(c) Read widely
CS IS cs " CS CM cs c> CI 1

;
s.s a
You will find many excellent text-books and 'popular' books on i E eoS a
Chemistry either at your school or in your public library. Every one c> c> ^ 1 ~H 1 cs CI ~* o '^.2 > S
of these will give you new ideas, presenting old material in a different 5> > o c

form. Chemistry is a 'live' subject and of increasing importance to

you in the civilised life you lead. Read about some of the applications i
cs cs ^4 CS 1 cs
1

^
1 1
'

and you will spend many interesting hours and widen and deepen
MM
O CS I

your knowledge. 1

cs CS 1
*— l 1 1 cs 1 cs

General statements
The following of statements of a general type is given purposely
list
i

CI C> cs ^H ~* CS cs CI - CI

without the common exceptions to them. Some are perfectly general

and others lejs so, but all are of wide application. Learn them and
o CI o - ^H CS cs 1 CS 1

attempt to write down (the symbols or formulae only will be quite

sufficient to test yourself) any substances which are exceptions to the
general statement. The exceptions are given on p. 523. i

-
t— C) CS
1
^ CS ro c> c> 1

1. Acids contain hydrogen which can be replaced by a metal.

2. Sodium, potassium and ammonium salts are soluble in water.
.a
3. Nitrates are soluble in water.
4. An ammonium salt heated with any alkali and water yields am-
* z u * ^ £ Dm a 5 Is
monia gas.
512 A NEW CERTIFICATE CHEMISTRY REVISION NOTES 513
5. Heavy metal carbonates yield the oxide and carbon dioxide Diagram A
when heated.
6. Heavy metal nitrates decompose under the action of heat to
yield the oxide, nitrogen dioxide and oxygen.
7. Metals are attacked by nitric acid.
8. The action of an acid on a carbonate is to yield carbon
dioxide.

Particular statements

The following list of questions summarises many of the unusual

facts which you are likely to overlook. Do not turn to the answers Example:
(p. 523) until you have tried them all. Gas Materials under equation Test
H, Zn + H.S04—* ZnSO« + H, Explodes with air when
1. What is the ONLY common alkaline gas? zinc dilute zinc hydrogen flame applied
2. What is the ONLY gas which turned brown on exposure to sulphuric
acid
sulphate

air?
3. What is the ONLY
common substance almost insoluble in
cold water but quite soluble in hot water?
4. What common substance increases its solubility in water very
little for a large increase
in temperature ? Fig. 162a.
5. What substances are LESS soluble in hot water than in
cold?
Diagram B
6. Which salts cannot be prepared, in solution, by the following
method?
l
acid -vSALT + water
or Skali}+

7. What are the 2 common insoluble chlorides?

8. What are the common insoluble sulphates?
9. What are the 3 common soluble carbonates?
10. What are the 4 common soluble metallic hydroxides?
11. What are the common amphoteric oxides?
(Answers on p. 523.)

If you would use a second wash-bottle, state in third column the liquid you
would put into it.
Common gases
Cos Materials under equation Test
There are about a dozen common gases.
Consider the following types of apparatus (Fig. 162). Look at them
for a few minutes and then close your book. Make a fair copy of each
one on a separate page of your exercise book. Under each diagram
make a table of gases which can be prepared using this type of
apparatus. (Some gases may come under two headings, according
Fio. 162b.
514 A NEW CERTIFICATE CHEMISTRY TESTS FOR RADICALS 515

Diagram C Common Names

Calcium sulphate* Plaster of Paris CaS04 .±H,0
Magnesium sulphate* Epsom salt MgS04 .7H2
Zinc carbonate Calamine ZnC03
Zinc oxide Zinc white ZnO
Zinc sulphate* White vitriol ZnS0 4 .7HjO
Zinc sulphide Zinc blende ZnS
IronOH) oxide* Rust; as ore, hsmatite Fej0 3 .nH,0
Tri-iron tetroxide Black oxide of iron Fe,0 4
Iron(II) sulphate* Green vitriol FeS04 .7Hs O
Lead(II) carbonate (basic] White lead Pb(OH) 2 .2PbC0 3
Lead(II) oxide Litharge PbO
LeadfJO sulphide Galena PbS
Trilead tetroxide Red lead Pb 3 4
CopperfJI) carbonate Malachite Cu(OH) a .CuC0 3
(basic)
Gas Coppcr(II) oxide Black copper oxide CuO
Copper(ri) sulphate* Blue vitriol CuS0 4 .5H 3
Copper(I) oxide Red copper oxide CujO
Carbon Black lead C
Sulphur Brimstone S
Hydrated.

Fig. 162c.
TESTS FOR ACID RADICALS IN SOLUTION
to state of purity required.) Fill in under the columns the
details
1. Sulphate radical
required. The answers are given on p. 522.
To
the solution of the suspected sulphate in water, add dilute
For any cases for which these diagrams do not apply draw a well-
hydrochloric acid and then barium chloride solution. white precipi- A
labelled sketch of the whole apparatus.
tate of barium sulphate indicates the presence of a sulphate in the
original solution. For example,
Common Names
Hydrochloric acid Spirits of salt HC1 BaCl 2 + Na 2 S0 4 ->- BaS0 4 + 2NaCl
Nitric acid Aqua fortis HNO, barium sodium barium sodium
Sulphuric acid Oil of vitriol H,S0 4 chloride sulphate sulphate chloride
Ammonium chloride Sal-ammoniac NH C1
4
(INSOLUBLE)
Potassium carbonate Pearl-ash K,CO,
Potassium hydroxide Caustic potash KOH ionically: Ba* + + SO, 2- ->- BaS0 4 j
Potassium nitrate Nitre, saltpetre KNO,
Sodium hydrogen Baking soda NaHCO, 2. {a) Chloride radical
carbonate
Sodium carbonate Soda-ash Na sCO, To the solution of the suspected chloride in water, add dilute nitric

Sodium carbonate* Washing soda Na B CO,.10H,O acid, followed by silver nitrate solution. A white curdy precipitate of
Sodium chloride Common salt NaCI silver chloride (soluble in ammonia) indicates the presence of the
Sodium hydroxide Caustic soda NaOH chloride radical in the original solution. For example,
Sodium nitrate Chile saltpetre NaNO,
NajSCvlOH.O AgNO a + KC1 -> AgCl
Sodium sulphate* Glauber's salt
Limestone, chalk, CaCO, I H KNO a
Calcium carbonate silver potassium silver potassium
marble, calcite nitrate chloride chloride nitrate
Calcium hydroxide Slaked lime Ca(OH), (INSOLUBLE)
Calcium oxide Lime, quicklime CaO
Calcium sulphate* Gypsum CaS0 4 .2H,0 ionically: Ag + + CI- ->- AgCI |
s
 ::

516 A NEW CERTIFICATE CHEMISTRY TESTS FOR RADICALS 517

(0) Bromide radical. Repeat as 2 (a) Flame coloration (see p. 374)

A
pale yellow precipitate of silver bromide, sparingly soluble in Potassium Lilac. Visible through blue glass.

ammonia, indicates the presence of a bromide. For example, Sodium Persistent golden yellow.
Calcium Brick-red.
AgN0 3 + NaBr -* AgBr J,
+ NaNO s
Copper Green or bluish green.
sodium silver
bromide bromide Lithium Carmine.
(INSOLUBLE)
ionically: Ag + + Br~ -> AgBr | Action of sodium hydroxide solution on solution of soluble salt of metal

Zinc salt. White precipitate of zinc hydroxide. Soluble in excess

(c) Iodide radical. Repeat as 2 (a)
of alkali. Precipitate ignited in crucible forms zinc oxide (yellow
yellow precipitate of silver iodide, insoluble in ammonia, indi-
A hot, white cold).
cates the presence of an iodide. For example
AgNO a + KI -
potassium
Agl |
silver
+ KNO, ZnS0 4 + 2NaOH Na 8 S0 4 + Zn(OH),
zinc
iodide iodide hydroxide

ionically: Ag+ + I- Agl | ionically: Zn2+ + 20H- Zn(OH) t J.

Nitrate radical
Zn(OH) g ZnO +H 2
3. zinc
oxide
(Brown ring test, see p. 436.) To the cold solution of the nitrate in

a boiling-tube add ferrous sulphate solution and (with care!) pour Iron. Iron(I[) salts. Green gelatinous precipitate of iron(II)
concentrated sulphuric acid steadily down the side of the tube. A hydroxide.
brown ring at the junction of the concentrated sulphuric acid layer Iron{III) salts. Reddish-brown gelatinous precipitate of
and aqueous layer proves the presence of a nitrate. iron(lll) hydroxide.
For example:
4. Carbonate radical FeSQ 4 -r 2NaOH Fe(OH) t + Na*S0 4
iron(Il)
Add dilute nitric acid to the substance in a test-tube (or to its hydroxide
solution in water). Effervescence is observed and carbon dioxide is
evolved which, if passed into lime-water, gives a white precipitate of ionically: Fe* + + 20H- Fe(OH) 2 \
chalk. For example, FeCl a + 3NaOH Fe(OH) s + 3NaCl
(iron(IH)
CuC0 3 + 2HN0 3 -> Cu(NO s) t + H,0 + CO a f hydroxide
carbon
dioxide ionically: Fes+ + 30H" - Fe(OH) 3 \
Lead(II) salts. White
precipitate of lead(ll) hydroxide soluble in
ionically: CuCO g + 2H + -»• Cu8+ + H fO + CO, | excess of alkali. Precipitate ignited in crucible forms lead oxide,
For sulphite test, see p. 409. a yellow powder.
For example
Pb(N0 3 ) s + 2NaOH -> 2NaNO + Pb(OH)
TESTS FOR BASIC RADICALS ionically: Pb2+ + 20H~ -> Pb(OH) j
s 2

s
The following some simple tests for the basic radicals present
are Pb(OH)e-*-PbO+H sO
in single salts (not mixtures). The metallic radicals are in combination,
not free as elements. Thus the test for potassium will be given by any Ammonium group, NH 4 . £01/ with sodium hydroxide solution. Am-
salt or compound of potassium. monia gas (turns red litmus blue) evolved.
518 A NEW CERTIFICATE CHEMISTRY ACTION OF HEAT 519

For example: Hydroxides

NH 4C1 + NaOH NH 3 -f H 2 + NaCl These decompose under action of heat (except sodium hydroxide
ammonia and potassium hydroxide) to give the oxide.
gas
Cu(OH) t ->-Cu0 4-H 2
ionically: NH 4
+ + OH~ +H -»• NH 3 \ 2

(NHJ 8 S0 4 + 2NaOH -*- 2NH + 2H 2 + Na 3 2 S0 4 Chlorides

be seen that the common metallic radicals
It will (if present singly) No action except on ammonium chloride, which sublimes and
can be detected either by dissociates.

(a) Flame coloration or NH 4Cl->-NH + HCl 3

(6) Action of sodium hydroxide solution.

Nitrates
Answer the following questions, using the above methods: (a) Sodium and potassium nitrates.

1. How would you show that potassium chloride contained 2KN0 3 -»- 2KNO a + 8
(a) potassium; (b) the chloride group? potassium oxygen
nitrite
2. How would you distinguish between zinc sulphate and sodium
sulphate? (b) Heavy metal nitrates, e.g.,
3. A dilute solution contains either iron(II) sulphate or iron(III) 2Pb(N0 3 ) 2 ->- 2PbO + 4NO + -
O, 2 (nitrates of silver
sulphate. How would you decide? lead(II) nitrogen oxygen and mercury
4. How would you distinguish between sodium nitrate and sodium oxide dioxide
decompose to
chloride?
metal)
5. A given black powder iscopper oxide or iron(II)
either black
sulphide. Explain how you would decide which of the two it is. (c) Ammonium nitrate.
6. A white powder is either potassium sulphate or potassium
NH N0 ->- N 2 + 2H
4 3 2
carbonate. How would you ascertain which it is ? dinitrogen water
oxide

Sulphates
ACTION OF HEAT ON COMMON SUBSTANCES
Basic oxides of metals
2FeSO d - Fe 2 3
- so 2 + so 3
iron(IT) iron(III) sulphur sulphur
No action except sulphate oxide dioxide trioxide

2HgO -> 2Hg +

2 (silver similarly)
Fe 2 (S04) 3 Fe 2 3 + 3SO a

mcrcury(ir) mercury oxygen iron (110 sulphate

oxide
Carbonates
Peroxides and dioxides of metals
All decompose except sodium and potassium carbonate, e.g.,
All decompose giving off oxygen (except sodium peroxide).
For example:
CuC0 3 -> CuO + C0 2
copper(II) copper(II) carbon
2H 2 2
- 2H 2 + 2
carbonate oxide dioxide
hydrogcn water oxygen
peroxide Bicarbonates or hydrogen carbonates
2Pb0 2 - 2PbO +O z decompose to give carbonate, water and carbon dioxide, e.g.,
lcad(IV) oxygen
oxide 2NaHCO.,— Na 2 C0 3 +>- H 2 + CO,
520 A NEW CERTIFICATE CHEMISTRY GAS PREPARATIONS 521
Ammonium salts
GAS PREPARATIONS: ANSWERS
These always decompose; sometimes sublime, e.g., ammonium
chloride.
The following remarks should be considered together with the
diagrams on pp. 513-14.
NH 4 C1
->• NH + HC1 3
ammonium
chloride
General notes on preparations of gases
Ammonium nitrate. See Nitrates.
1. Do not collect gases of approximately the same density as air
by displacement of air. If the gases are required dry they must be
Metals
dried by a suitable substance and collected over mercury. This refers
All metals oxidise if heated in air, except silver and gold, to form to O t N a O, NO, N2
, .

BASIC OXIDES, e.g., The

following gases may be dried with concentrated sulphuric acid
2Ca + Cv ->2CaO (symbol or formula only given):
calcium calcium
oxide 2 H, N. N2 HC1 C0 2 SO s Cl 2 CO
2Mg + Cv -»-2MgO
For the following, use special drying agents.
magnesium magnesium
oxide Ammonia - quicklime.
Hydrogen sulphide- calcium chloride (quite satisfactory in
Non-metals practice).
Carbon, phosphorus and sulphur combine with the oxygen of the
air to form ACIDIC OXIDES. For example: 2. NEVER DRY A GAS AND THEN COLLECT IT
S + 2
-* S0 2 OVER WATER.
sulphur sulphur
dioxide
3. Draw your diagrams with the following points in mind.
Miscellaneous (a) The apparatus stands on
the bench. Do not draw, for
example, a wash-bottle in mid-air.
Hydrates (that is, salts possessing water of crystallisation) give off
(b) Show a clear way through for the gas to pass. A diagram
water vapour. For example:
should be a section and not a pictorial illustration. Do not
Na ? CO 3 .10H 2 O - Na 2C0 3 + 10H 2 O waste time on non-essentials.
sodium carbonate anhydrous water
crystals sodium (c) Label the diagram clearly. It makes a description much
carbonate briefer and leaves no room for doubt.
Potassium chlorate. (d) Indicate simply how the apparatus is supported, for example,
tripod and gauze, clamps, etc.
2KC10 3 -> 2KC1 + 30,
potassium potassium oxygen
chlorate chloride
4. If a steady supply of a dry gas is wanted (for example,
hydrogen,
Red lead. or carbon monoxide for reduction of oxides) a calcium chloride
tube
2Pb 3 4
- 6Pb0 + 2 isto be preferred, as the drying apparatus, to a Woulff's bottle
con-
red lead litharge oxygen
taining concentrated sulphuric acid. The latter gives a jerky supply
of the gas, the former a steady supply.
5. Give the equation for the reaction concerned
on or near the
diagram. It is then clear to which action the equation refers, and
you
have then completed two of the important steps in the description
of
any chemical process.
522 A NEW CERTIFICATE CHEMISTRY GAS PREPARATIONS 523
Diagram A. Flask, thistle funnel— no heat—collect over water. Diagram C. Hard glass tube or small flask. Collect over water.
Cu Materials under Equation Test Gas Materials under Equation Test

H, Zn + H.S04- ZnSO« + H, Explodes with air when MnO,

zinc dilute zinc hydrogen flame applied. O, 2KC10, * 2KC1 + 30, Rekindles glowing splint
sulphuric add sulphate potassium
chlorate
potassium
chloride
oxygen — not soluble in water.
H.S FeS-f 2HC1- FeCl, + H,S Blackens lead(II) acetate
iron(ll) fairly cone,
sulphide hydrochloric
iron(ll)
chloride
hydrogco
sulphide
paper. N, NH.NO,-
ammonium
> N, -f- 2H.O Inert gas. Gives negative
nitrogen steam testwith splint and
•eld nitrite
lime-water.
CO, CaCO, + 2HC1 — • CaCI, + H,0 + CO, Turns lime-water turbid.
solution

marble dilute calcium carbon N.O NH.NO, —> N,0 + 2H.O Rekindles glowing splint
hydrochloric
acid
chloride dioxide ammonium
nitrate
dinitrogen
oxide
steam — soluble in cold water.
(do not heat flask
NO 3Cu + 8HNO.-H 3Cu(NO,), + to dryness)
copper fairly cone, copper
nitric acid nitrate
4H.O + 2NO Forms brown fumes on
nitrogen exposure to air. Special diagrams for ammonia and carbon monoxide. (See pp. 426,
monoxide
299.)
CI, 2KMnO, + 16HCI—»-2KCI +
potassium cone potassium Answers to general statements
permanganate hydrochloric chloride
acid
2MnCl, + 8H.0 + SCI, Bleaches damp litmus
(N.B. Common exceptions only given.) (See p. 510.)
chlorine (greenish-yellow gas) 1-5. No exceptions.
(Collect over brine.) 6. Silver nitrate yields the metal. MercuryfJI) nitrate similar.

Diagram B. Flask heated, wash-bottles, collect by displacement of

2AgN0 3 -> 2Ag + 2NO, + (
7. With concentrated becomes 'passive' (see p. 488).
nitric acid iron
air.
8. Certain salts, being insoluble, form a protective layer round the
Gas Materials under Equation Test carbonate, preventing the action of the acid. For example:
calcium carbonate and dilute sulphuric acid, barium carbonate
HCl NaCl + H.SO, —* NaHSO, + HCl Gives white precipitate of and dilute sulphuric acid.
sodium cone. sodium hydrogen AgCl with silver nitrate
chloride sulphuric hydrogen chloride
acid sulphate in nitric acid solution. Answers to particular statements
(Heat not essential.) (Concentrated sulphuric
acid in wash-bottle.) (N.B. Common exceptions only given.)
1. Ammonia.
SO a Cu-h 2H,S<V CuSO, + 2H.O + SO, Decolorises potassium
Nitrogen monoxide.
copper hot cone, sulphur permanganate without 2.
sulphuric dioxide
acid precipitate of sulphur. 3. Lead(Il) chloride.
(Concentrated sulphuric 4. Common salt.
acid in wash-bottle.)
5. Calcium hydroxide. Sodium sulphate (over a certain tempera-
CI, MnO, -I 4HC1 — > MnCl, + 2H.O + CI, Bleaches damp litmus. ture range).
man- cone. manganese chlorine (Water in first bottle and
gancse hydrochloric chloride 6. Lead(II) chloride, lead(II), calcium and barium sulphates.
dioxide acid (or concentrated sulphuric
common salt acid in second.) (Carbonates are not usually prepared by this method.)
and cone, Chlorine attacks mercury.
sulphuric acid) 7. Silver chloride, lead(II) chloride.
8. Lead(IT) sulphate, barium sulphate.
CO H.C.O. - H.O -> CO + CO, Burns with blue flame to
oxalic acid and carbon carbon carbon dioxide (pass 9. Sodium, potassium and ammonium carbonates.
cone sulphuric monoxide dioxide
acid to remove through two bottles of 10. Sodium, potassium, ammonium and calcium hydroxides. (Cal-
the elements caustic potash solution cium hydroxide is only slightly soluble.)
of water and collect over water).
11. Zinc oxide, lead(II) oxide, aluminium oxide.
 DEFINITIONS 525

Double decomposition is an action of the type

AX + BY-*AY + BX
where A, B represent metallic radicals and X, Y non-metallic or
acidic radicals.
Definitions
Dulong and Petit's Law states that
Atomic Weight of a solid element X Specific Heat of the element
Acid a substance which, in aqueous solution, yields hydrogen ion,
is
= 6.4 (approx.)
Efflorescence the giving up of water of crystallisation by a crystal
H
+ , as the only positive ion. It hydrates to
3
+ H .
is

Alkali is a base which is soluble in water. to the atmosphere.

Electrolysisis the decomposition of a compound, molten or in solu-
Allotropy. If the same element can exist, without changing its state,
in two or more different forms, the element is said to exhibit by the passing of an electric current
tion,

allotropy. These various

forms are termed allotropes. Equivalent of an element is the number of parts by weight of the
Amphoteric oxide (hydroxide) is one which exhibits both basic and element which combine with or displace 8.000 parts by weight of
acidic properties. oxygen (or 1.008 parts by weight of hydrogen or 35.46 parts by
Analysisis the splitting up of a chemical compound into its element- weight of chlorine). (See Mole.)
ary or simpler substances. Gay-Lussac's Law. Gay-Lussac's law of combining volumes states:
Anhydride is an acidic oxide of a non-metal. When gases react, they do so in volumes which bear a simple
Atom is the smallest indivisible particle of an element which can take ratio to one another, and to the volume of the product if gaseous,

part in a chemical change. temperature and pressure remaining constant.

Atomic weight of an element is the mass of one atom of the element G.M.V. The Gram-Molecular Volume of any gas is the volume
on a scale which gives a mass of 12 units (exactly) to one atom occupied at s.t.p. by its gram-molecular weight, and is 22.4 dm*
of carbon-12, 12
C. (litres). (Also called molar volume.)
Avogadro constant (often called Avogadro number) is the number Hydrolysis a double decomposition between a salt and water, the
is

of atoms contained in 12 g of carbon-12. This number is hydroxyl group of the latter remaining intact.
6.02 X 10". AB + HOH-»-HB + AOH
Avogadro's Law states that 'equal volumes of all gases under the same Law of Constant Composition. All pure samples of the same chemical
conditions of temperature and pressure contain the same number compound contain the same elements combined in the same
of MOLECULES*. proportions by mass.
Base a substance which can combine with hydrogen ion,
is
+. H Law of Indestructibility of Matter (Conservation of mass). Matter is
Basicity of an acid is the number of hydrogen ions, , H
+ which the
neither created nor destroyed in the course of chemical action.
acid can produce per molecule. A
Law of Multiple Proportions states, if two elements and B combine
Boyle's Law states that the volume of a given mass of gas is in-
together to form more than one compound, then the several
versely proportional to pressure, temperature remaining
its
masses of which separately combine with a fixed mass of B
A
constant.
are in a simple ratio.
Molar (M) Solution of a compound, X, contains one mole of X in
Catalyst a substance which, although present in small proportion,
is
A
speed of chemical reaction but remains chemically un-
alters the
one dm 3 of solution.
changed at the end of the reaction.
Mole of any substance is the amount of it which contains as many
Charles' Law. For a given mass of gas the volume is proportional to
elementary units as there are atoms in 12 g of carbon-12. (This
the kelvin (absolute) temperature (pressure constant). 23
number is the Avogadro constant, 6.02 X 10 .)
Deliquescence is the absorbing of moisture from the atmosphere by a term mole has led to many changes of
The adoption of the
solid to form a solution.
nomenclature. The Table (p. 526) illustrates a few.
Diffusion is the process by which a gas fills the whole of a vessel into 23
All these mole quantities contain 6.02 X 10 (Avogadro con-
which it is placed. concerned.
stant, often called Avogadro number) of the particles
524
526 A NEW CERTIFICATE CHEMISTRY DEFINITIONS 527

lilcmcntary units
Amount of substance Synthesis is the building up of a compound from elementary or
concerned New name simpler substances.
Old name
Thermal dissociation is the decomposition of a compound by the

Compound molecules one mole of action of heat. If the products are allowed to cool they will
one gram-molecule
or element molecules reform the original substance.
Element atoms one mole of one gram-atom Valency of an element is the number of hydrogen atoms which will

Ion ions
atoms
one mole of
combine with or displace ONE ATOM of the element.
one gram-ion
ions
Water of crystallisation is that definite amount of water with which
Electrons electrons one mole of one faraday some substances are associated on crystallising out from an
electrons (96 500 coulombs aqueous solution.
approx.)
1H.SO, one mole of one gram-
iH,SO, equivalent of Oxidation number.
sulphuric acid
The state of oxidation of an element in a compound is sometimes
indicated by an oxidation number. Atoms in a free element have an
Molecule of an element or compound is the smallest particle of it oxidation number of zero. When a simple ion is formed, the element
which can normally exist separately. assumes an oxidation number with the same sign as the ionic charge;
Molecular weight of a compound (or element) is the mass of one its numerical value is the same as the number of electrons lost or

molecule of the compound (or element) on a scale which gives
a mass of 12 units (exactly) to one atom of carbon-12, 12 C. (See
Mole.)
Neutralisation is a reaction in which hydrogen ion, H + or hydroxon-
,
ium ion, H 3 0-, derived from an acid, and hydroxyl ion, OH~,
gained when the ion is formed from the atom. For example, as copper(IT)
ion, Cu ,+ , the copper has an oxidation number of +2; as sulphide ion,
S a ~, sulphur has an oxidation number of —2. When oxidation occurs, the
oxidation number of the element is increased, the sign being always taken
into account. For example, the oxidation
Fe«+ -e-—»-Fe + s

derived from a hydroxyl base, combine to form water. raises the oxidation number of iron from +2 to +3; correspondingly,
H+ + OH- ^H 2
the oxidation

Normal solution one which contains the equivalent weight of

is
S*"—»-S +2e~
a
substance in grams in 1 litre of solution. raises the oxidation number of sulphur from —2 in the ion to zero as
element. Reduction correspondingly reduces the oxidation number.
Oxidation is the process of electron loss.
The charge on a complex ion is the algebraic sum of the oxidation
-
Reduction is the process of electron gain. numbers of its constituent atoms. In the ion, MnO« , manganese is in
Salt is a compound consisting of positive metallic ions and negative the oxidation state of +7 (corresponding to oxide, MnjO,) and oxygen of
ions derived from an acid if the negative ions are capable of
;
—2. The expression, 7 + 4(-2), gives the residual ionic charge of —1.
+ In S<V~, the sulphur has to be taken as positive relative to oxygen and
further ionisation to yield H the salt is an acid salt, but, if not,
,
existing in the +6 oxidation state (corresponding to SO,). Then the
the salt is a normal salt. ionic charge is given by the expression:
Saturated solution of a solute at a particular temperature is one which 40'- ->• SO,*-.
S«+ +
contains as much of the solute as it can dissolve at that tempera-
The 'ion',S,+, is, however, only an imaginary particle. Oxidation of an
ture, in the presence of solid particles of the solute. compound) raises the oxidation number of one at least of its
ion (or
Solubility of a solute in a solvent at a particular temperature is the constituent elements, while reduction brings a corresponding fall.

number of grams of solute necessary to saturate 100 g of the

solvent at that temperature.
s.t.p. or N.T.P. 'Standard' or 'Normal' temperature and pressure,

that is, 0°C and 760 mmof mercury.

Super-saturated solution. A
solution is said to be super-saturated when
itcontains in solution more of the solute than it can hold at that
temperature in the presence of the crystals of the solute.
 GENERAL QUESTIONS 529
Which of the following statements is true: the Avogadro number is
10.
(i) number of electrons in a gram-atom of any solid element, (ii) the
the
number of atoms in a gram-molecule of any gas at s.t.p., (iii) the number
of atoms in a gram-atom of any element, (iv) the number of electrons
needed to liberate one gram of a univalent metal in electrolysis, (v) the
General Questions number of protons in a gram-atom of any element?
11. Which of the following statements is true: an aqueous solution of
(including Multiple Choice) pH = 6 is (i) neutral, (ii) slightly acidic, (iii) strongly alkaline, (iv) strongly
acidic?
12. Which of the following statements is true: an aqueous liquid of
1.Equal volumes of oxygen and hydrogen are weighed at constant pH = 8 is (i) slightly alkaline, (ii) neutral, (iii) strongly acidic, (iv) weakly
temperature and pressure. The weights are oxygen, x g, and hydrogen y g. acidic?
Select the correct statement from the following: (i) x = y, (ii) x = 2y,
13. Which of the following aqueous solutions is most likely to liberate
(iii) x = x = I6y, (v) x = $y.
8y, (iv) hydrogen by the action of magnesium powder, a solution of (i) pH = 7,
2. A certain atom has atomic number, Z, and mass number, A. Select pH = pH =
(ii) 2, (iii) 12, (iv) pH = 6.5?
the correct statements from the following.
Which of the following aqueous
solutions is most likely to liberate
(a) The number of neutrons in the atom is (i) Z — A, (ii) A — Z,
14.
hydrogen by the action of aluminium powder, a solution of (i) pH = 13,
(iii) A + Z. (ii) pH = 7, (iii) pH = 7.4?
(b)The number of protons in the atom is (i) A, (ii) Z, (iii) {(A + Z).
(c) The number of electrons in the atom is (i) Z, (ii) Z + A, (iii) A.
15. Two gaseous compounds, A and B, have molecular weights of 2
and 50 respectively. In the same conditions, how many times faster does A
3. The ammonia molecule forms a valency bond with hydrogen ion.
diffuse than B: (i) 25 times, (ii) 12i times, (iii) 5 times, (iv) 100 times?
Which one of the following statements is true: the bond (i) results from an
electron pair equally shared, (ii) results from a pair of electrons donated 16. Equal volumes of M
hydrochloric acid and sulphuric acid are M
by the ammonia molecule, (iii) is an electrovalent bond, (iv) results from neutralised by dilute sodium hydroxide solution and x kcal and y kcal of
a pair of electrons donated by the hydrogen ion ? heat are liberated respectively. Which of the following is true: (i) x — y,
4. Elements X Y
are in Group II and in Periods 2 and 3 of the
and (»)* = iv, (HO* = lyl
Periodic Table. Which of the following statements is true: (i) and areX Y Equal volumes of
17. M
hydrochloric acid and sulphuric acid are M
both electronegative elements, (ii) X and Y can both ionise by losing two by dilute solutions of sodium hydroxide and potas-
neutralised separately
electrons per atom, (iii) X and Y
arc equally electropositive, (iv) and Y X sium hydroxide. The heat evolved in each case is:
have equal electrical conductivities? M-HC1—NaOH a kcal M-HC1— KOH b kcal
5. Which of the following statements is correct sulphur is classified as
: M-H,S04 — NaOH c kcal M-H,S04 — KOH d kcal.
a non-metal because (i) it has a low m.p., (ii) it is an electronegative element, Which of the following statements are true: (i) a = b, (ii) a = c,
(iii) it is much less dense than most metals, (iv) it forms a stable hydride? (iii) c = d, (iv) b = d, (v) a - dl

6. Which of the following statements is correct: iron is classified as a 1 8. Consider the reaction
metal because (i) it is an electropositive element, (ii) it is much denser than
any non-metal, (iii) it forms a solid chloride, (iv) it shows two states of iCl 1 -rI-^-Cl-+iI,
oxidation? Which of the following statements are true with respect to it: (i) chloride
7. Atoms A
and B arc isotopes of the same element. Which of the follow- ion a reducing agent, (ii) chlorine is an oxidising agent, (ii) iodide ion is
is
ing statements are true: A and B have (i) the same number of electrons, oxidised, (iv) iodine is an oxidising agent?
(ii) the same mass number, (iii) the same number of protons, (iv) the same 19. A and B are atoms of elements in the same early period of the Periodic
number of neutrons, (v) the same number of electrons in the highest energy Table; A is in Group II and B in Group m. Which of the following state-
level? ments are true: (i) B has one more proton in its nucleus than A, (ii) the
8. Which of the following statements is true: magnesium is a good atomic weight of B must be one unit greater than the atomic weight of A,
conductor because (i) it can be formed into filaments, (ii) its
electrical (iii) A has one electron fewer than B in the highest energy level, (iv) B must
atoms contain positively charged nuclei, (iii) some of its electrons arc free have one neutron more than A in its nucleus, (v) A contains one electron
to move through the metal, (iv) it is extracted from its chloride by electro- fewer than B?
lysis? 20. A and B are atoms of elements in the same Group of the Periodic
9. Which of the following statements is true: sulphur
a very poor
is Table. A is in Period 2 and B in Period 3. Which of the following state-
electrical conductor because (i) it is less dense than most metals, (ii) its ments is true: (i) A and B have equal numbers of protons in their nuclei,
atoms contain positively charged nuclei, (iii) its electrons are tightly bound (ii) A and B have equal numbers of electrons in their highest energy levels,
to atomic nuclei, (iv) it cannot be formed into filaments at room tem- (iii) A and B must have equal numbers of neutrons in their nuclei, (iv) A
perature? has two electrons, and B three electrons, in its highest energy level?
528
530 A NEW CERTIFICATE CHEMISTRY
21. Explain the following facts: (a) aqueous hydrogen chloride is
strongly acidic while a solution of the gas in pure toluene is non-acidic;
(b) methane is gaseous while sodium chloride is a solid at room temperature
and pressure; (c) diamond is hard and very resistant to attack by chemicals,
while graphite is soft and less resistant to chemical attack; (d) copper
conducts electricity readily, sulphur hardly at all. Answers to Numerical Examples
22. The halogen
elements, chlorine and bromine, both show: (a) uni-
valency; (b) oxidising action. Explain this in electronic terms. Give one (Using the approximate atomic weights as given on p. 532)
example of the oxidising action of chlorine and one (different) example of
the same for bromine, mentioning experimental conditions. Give evidence
to show that chlorine is the stronger oxidising agent. How does the silver
salt of bromine behave on exposure to light?
Chapter 2, p. 23.
8. X.O..
23. The atom of an element, X, has electron shells 2,8,8,2. Without
identifying the element, discuss, in electronic terms: (a) the valency of the
Chapter 3, p. 31.
element; (_b) whether it is likely to have oxidising or reducing properties; 1. 2:3. 5. 1:2. 11. 50.7g,25.4g, 13. 18.7g.28.0g,
(c) the likely nature and formula of its chloride; (</) the likely nature,
2. 4:2:1. 6. 1:2. X.O. MCI„MSO«.
formula and solubility in water of its hydroxide. Suggest with reasons a 3. 1:2. 8. 25.5, 2.8, 1 2. 64 1 28 g, 14. 37.3 g, 56.0 g,
1 g,
likely method of extraction of the element on the large scale.
4. 1:2. 1:2. 64g,M,0, MCI,.
of periodicity as applied to chemical elements by
24. Illustrate the idea MO.
reference to the elements sodium, nitrogen, chlorine, potassium, fluorine
and phosphorus. Quote the electronic structures of their atoms and give Chapter 5, p. 44.
at least two examples of periodicity of properties among them. (a) 253.3 cm'. (e) 570 cm 3 . (/) 51.2 cm 3 .

25. Two metals, A and B, are both divalent and without action on water. (b) 1638 cm 3 . (/) 637 cm
3
. 0") 626 cm 3 ,

A is much the more electropositive. Explain,

in electronic terms, what you (c) 1110 cm 3 .
(g) 641.5 cm
3
. (it) 76.1 cm'.
would expect happen if A is placed in a solution of a salt of B. What
to (d) 450 cm 3 . (/0 133.5 cm 3 . (/) 118.2 cm 3 .

arrangement could be made, involving A and B, to obtain electric current? (/n) 518.4 cm 3 .

Explain how the arrangement works and why it would probably be unsuit-
able for giving current over a long period. Suggest, with reasons, likely Chapter 6, p. 51.
forms in which A
and B would occur in nature and likely means of extract- 1. Cu.O. 7. PbO, PbO-. 12. 0.5%.
ing the metals. 2. 2:1. 8. 2 and 3. 13. 0.53 g.
3. 24. 9. 3. 14. 9, 27.
26. Give two examples of photocatalysis, one from organic and one
(a)
from inorganic chemistry; (b) one example each of an exothermic reaction 4. MgO. 10. M.O,. 15. 99.5.

and an endothermic reaction; (c) two reasons for considering air to be a 5. Al,O a . 11. MCI,. 16. 28; 18.7.

mixture; (d) one example of an isotopic element, explaining the occurrence

of the isotopes. Why, in spite of isotopy, does such an element usually have
Chapter 7, p. 60.
1. 15.875 tonnes. (d) 29.11%. 10. 3.286 oz.
only very slight variations of atomic weight?
2. 1.55 g. 40.51%. 11. 73 g.
27. Outline the manufacture of calcium carbide. What is meant by calling ZnCl,.
3. 30.38%. 12. 3.036.
this an electrothermal reaction? In contrast, describe the electrolytic
NaCI. 5. 63 g. 13. CaC1..2NH,.
extraction of calcium and explain the between the
essential differences CuSO,. 6. 2.67 g. 2.24 dm 3 .

two methods. Contrast the behaviour of cold water with calcium and PbN,0,. 7. 20.04 g. 14. 97.5%.
calcium carbide. 4. (a) 27.38%, 1.19%. 40.08 15. 80.85 cm 3
g. .

28. The essential reaction for the Haber process is: 14.29%, 57.14%. 8. 3.085 g. 0.1601 g.

N + 3H ^ 2NH,; A kcal evolved (b) 36.04%, 63.96%. 9. 15.89 g. 90.91%.

3 2
(c) 21.21%, 6.06%. slaked lime
Deduce the conditions required to produce the greatest degree of efficiency 24.24%, 48.48%. by 5.42 g.
in the conduct of the process and indicate briefly how they are realised in
practice. How is the ammonia extracted after production? How is it Chapter 9, p. 110.
converted to nitric acid on the large scale? 1. 17 g. 34 g. 4. 1.083 dm 3 . 8. 7.167 g.
29.Give a concise account of the chemistry of the chlorides, oxides and 28 g. 71 g. 5. 71. 8.336 g.
hydrides of nitrogen and phosphorus (excluding preparations) to show 44 g. 6. 1.551 dm 3
. 10. 4 atoms.
that these two elements are properly included in the same group. Relate 2. 32, 64, 30. 7. 100 cm 3 . 11. 124.
your answer as much as possible to electronic considerations. 3. 33.6 dm 3
. 60%. 13. 1.63 g 36.2.
531
532 A NBW CERTIFICATE CHEMISTRY LOGARITHMS
Chapter 10, p. 122.
6. 0.5152 g.
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Chapter 11, p. 132.
1. 0.25 M. 6. 24.5 cm'. 10. 0.667 M. 10 0000 0043 0086 0128 0170 0212 0253 0294 033-1 0374 '•
8 12 17 21 25 29 33 37
2. 6.27 g. 7. 0.217 M. 11. 20.83 cm'.
11 0414 0453 0492 0531 0569 0607 0645 0682 0719 0755 4 8 11 15 19 23 26 30 34
3. 0.0714 M. 7.92 g. 0.833 M. 12 0792 0828 0864 0899 0934 0969 1004 1038 1072 1106 3 7 10 14 17 21 24 28 31
4.00 g. 8. 0.13 M. 12. 197 cm'. 13 1139 1173 1206 1239 1271 1303 1335 1367 1399 1430 3 6 10 13 16 19 23 26 29
4. 25 cm'. 12.7 g.
14 1461 1492 1523 1553 1584 1614 1644 1673 1703 1732 3 6 12 15 18 21 24 27
5. 18.75 cm'. 9. 418 cm'; 0.99 M. 2014
15 1761 1790 1818 1847 1875 1903 1931 1959 1987 3 6 .s 11 14 17 20 22 25
16 2041 2068 2095 2122 2148 2175 2201 2227 2253 2279 3 5 B 11 13 16 18 21 24
Chapter 16, p. 240.
6. 7 mols. 8. 993.3 cm'. 496.7 cm'. 17 2304 2330 2355 2380 2405 2430 2455 2480 2504 2529 2 5 7 10 12 15 17 20 22
18 2553 2577 2601 2625 2648 2672 2695 2718 2742 2765 2 5 7 9 12 14 16 19 21
Chapter 19, p. 271. 19 2788 2810 2833 2856 2878 2900 2923 2945 2967 2989 2 4 7 9 11 13 16 18 20
1. 9.82g (using G.M.V.). 4 8 11 13
3201 2 6 15 17 19
4. 68.5% of original mixture. 57.4% N„ 42.6% H t.
20 3010 3032 3054 3075 3096 3118 3139 3160 3181

21 3222 3243 3263 3284 3304 3324 3345 3365 3385 3404 2 4 6 8 10 12 14 16 18
Chapter 20, p. 278. 22 3424 3444 3464 3483 3502 3522 3541 3560 3579 3598 2 4 6 8 10 12 14 15 17
6. 14.4. 23 3617 3636 3655 3674 3692 3711 3729 3747 3766 3784 2 •1 6 7 9 11 13 15 17

Chapter 21, p. 285. 24 3802 3820 3838 3856 3874 3892 3909 3927 3945 3962 2 4 5 7 9 11 12 14 16

4. (b) 8.4 dm 3
5. 20 cm'. 90 cm'. 0.2268 25 3979 3997 4014 4031 4048 4065 4082 4099 4116 4133 2 3 7 9 10 12 14 15
. g.
26 4150 4166 4183 4200 4216 4232 4249 4265 4281 4298 2 3 s 7 8 10 11 13 15
Chapter 23, p. 317. 4440 4456 2 3 6 8 9 13 14
27 4314 4330 4346 4362 4378 4393 4409 4425 5 11
3. 37.12%. 10. 10.5 vols.
28 4472 4487 4502 4518 4533 4548 4564 4579 4594 4609 2 3 5 6 8 9 11 12 14
29 4624 4639 4654 4669 4683 4698 4713 4728 4742 4757 1 3 4 6 7 9 10 12 13
Chapter 28, p. 385.
9. 50.0 cm'. 11. 6.234 dm'. 30 4771 4786 4800 4814 4829 4843 4857 4871 4886 4900 1 3 4 6 7 9 10 11 13

31 4914 4928 4942 4955 4969 4983 4997 5011 5024 5038 1 3 4 6 7 8 10 11 12
Chapter 31, p. 421.
32 5051 5065 5079 5092 5105 5119 5132 5145 5159 5172 1 3 4 5 7 8 9 11 12
5. 6.604%. 5263 5289 5302 4 6 8 9 10 12
33 5185 5198 5211 5224 5237 5250 5276 1 3 5

Chapter 34, p. 453. 34 5315 5328 5340 S353 5366 5378 5391 5403 5416 5428 1 3 4 5 6 8 9 10 11
6. 1.4 dm' N.O. 1.6 dm' NO. 35 5441 5453 5465 5478 5490 5502 5514 5527 5539 5551 1 2 4 5 6 7 9 10 11
36 5563 5575 5587 5599 5611 5623 5635 5647 5658 5670 1 2 4 5 6 7 8 10 11

37 5682 5694 5705 5717 5729 5740 5752 5763 5775 5786 1 2 3 5 6 7 8 9 10
38 5798 5809 5821 5832 5843 5855 5866 5877 5888 5899 1 2 3 5 6 7 8 9 10
39 5911 5922 5933 5944 5955 5966 5977 5988 5999 6010 1 2 3 4 5 7 8 9 10
List of Approximate Atomic Weights 40 6021 6031 6042 6053 6064 6075 6085 6096 6107 6117 1 2 3 4 5 6 8 9 10

41 6128 6138 6149 6160 6170 6180 6191 6201 6212 6222 1 2 3 4 5 6 7 8 9
Aluminium 27 Magnesium 24 42 6232 6243 6253 6263 6274 6284 6294 6304 6314 6325 i 2 3 4 5 6 7 8 9
43 6335 6345 6355 6365 6375 6385 6395 6405 6415 6425 1 2 3 4 5 6 7 8 9
Barium 137 Manganese 55
Bromine 80 Mercury 200 44 6435 6444 6454 6464 6474 6484 6493 6503 6513 6522 I 2 3 4 5 6 7 8 9
45 6532 6542 6551 6561 6571 6580 6590 6599 6609 6618 1 2 3 4 5 6 7 8 9
Calcium 40 Nitrogen 14 46 6628 6637 6646 6656 6665 6675 6684 6693 6702 6712 1 2 3 4 5 6 7 7 8
Carbon 12 Oxygen 16
6803 6
47 6721 6730 6739 6749 6758 6767 6776 6785 6794 1 2 3 4 S 5 7 8
Chlorine 35.5 Phosphorus 31 I
48 6812 6821 6830 6839 6848 6857 6866 6875 6884 6893 1 2 3 4 4 5 6 7 8
Chromium 52 Platinum 195 49 6902 6911 6920 6928 6937 6946 6955 6964 6972 6981 1 2 3 4 4 5 6 7 8

Copper 63.5 Potassium 39 50 16990 6998 7007 7016 7024 7033 7042 7050 7059 7067 1 2 3 3 4 5 6 7 8
Hydrogen 1 Silver 108 51 7076 7084 7093 7101 7110 7118 7126 7135 7143 7152 1 2 3 3 4 5 6 7 8
Iodine 127 Sodium 23 52 7160 7168 7177 7185 7193 7202 7210 7218 7226 7235 ! 2 2 3 4 5 6 7 7
S3 |7243 7251 7259 7267 7275 7284 7292 7300 7308 7316 1 2 2 3 4 S 6 6 7
Iron 56 Sulphur 32 [

Lead 207 Zinc 65 54 7324 7332 7340 7348 7356 7364 7372 7380 7388 7396 1 2 :: 3 4 5 6 6 7

° 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
1
 LOGARITHMS International Atomic Weights
The following atomic weights are based on the exact number 2 for the carbon isotope 2, as agreed
1 1

between the International Unions of Pure and Applied Physics and of Pure and Applied Chemistry.
| 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Sym- At. Sym- At.
55 7404 7412 7419 7427 7435 7443 7451 7459 7466 7474 i 2 2 3 4 5 5 6 7 Name bol No. At. wt. Name bol No. At. wt.
56 7482 7490 7497 7505 7513 7520 7528 7536 7543 7551 i 2 2 3 4 5 5 6 7 Actinium Ac 89 — Mercury Hg 80 200.59
Aluminium Al 26.9815 Molybdenum Mo 42 95.94
57
58
7559
7634
7566
7642
7574
7649
7582
7657
7589
7664
7597
7672
7604
7679
7612
7686
7619
7694
7627 l 2 2 3 4 5 5 6 7 Amcricium Am
13
95 — Neodymium Nd 60 144.24
7701 1 2 3 4 4 5 6 7 Antimony Sb 121.75 Neon Ne 10 20.183
59 7709 7716 7723 7731 7738 7745 7752 7760 7767 7774
!

1 1 2 3 4 4 5 6 7 Argon Ar
51
18 39.948 Neptunium Np 93 —
Arsenic As 33 74.9216 Nickel Ni 28 58.71
60 7782 7789 7796 7803 7810 7818 7825 7832 7839 7846 i 1 2 3 4 4 5 6 6 Astatine At 85 — Niobium Nb 41 92.906
Barium Ba 56 137.34 Nitrogen N 7 14.0067
61
62
7853
7924
7860
7931
7868
7938
7875
7945
7882
7952
7889 7896 7903 7910 7917 1 1 2 3 4 4 5 6 6 Bcrkclium Bk 97 — Nobclium No 102 —
7959 7966 7973 7980 7987 ! 1 2 3 3 4 5 6 6 Beryllium Be 4 9.0122 Osmium Os 76 190.2
63 7993 8000 8007 8014 8021 8028 8035 8041 8048 8055 1 1 2 3 3 4 5 5 6 Bismuth Bi 83 208.980 Oxygen O 8 15.9994 ±0.000
Boron B 5 10.811 ±0.003* Palladium Pd 46 106.4
64 8062 8069 8075 8082 8089 8096 8102 8109 8116 8122 1 2 3 4 5 5 6 79.909' Phosphorus P IS 30.9738
1 3 Bromine Br 35
65 8129 8136 8142 8149 8156 8162 8169 8176 8182 8189 2 3 4 Cadmium Cd 48 112.40 Platinum Pt 78 195.09
66 8195 8202 8209 8215 8222 8228 8235 8241 8248 8254
1

1
1
1 2
3

3 3 4
5
5
5
5
6
6 Ctesium Cs 55 135.905 Plutonium Pu 94 —
—
Calcium Ca 20 40.08 Polonium Po 84
67
68
8261
8325
8267 8274
8338
8280
8344
8287 8293 8299 8306 8312 8319 1 1 2 3 3 4 5 5 6 Californium Cf 98 — Potassium K 19 39.102
8331 8351 8357 8363 8370 8376 8382 1 1 2 3 3 4 4 5 6 Carbon C 6 12.01115 ±0.00005 Praseodymium Pr 59 140.907
69 8388 8395 8401 8407 8414 8420 8426 8432 8439 8445 1 1 2 2 3 4 4 5 6 Cerium Ce 58 140.12 Promcthium Pm 61 ^_
Chlorine CI 17 35.453* Protoactinium Pa 91
70 8451 8457 8463 8470 8476 8482 8488 8494 8500 8506 I 2 2 3 4 4 Chromium Cr 24 51.996' Radium Ra 88
8513
1 5 6
Cobalt Co 27 58.9332 Radon Rn 86 —
71 8519 8525 8531 8537 8543 8549 8555 8561 8567 1 2 2 3 4 4 5 5 Copper Cu 29 63.54 Rhenium Re 75 186.2
72 8573 8579 8585 8591 8597 8603 8609 8615 8621 8627 1
1

1 2 2 3 4 4 5 5 Curium Cm 96 — Rhodium Rh 45 102.905

73 8633 8639 8645 8651 8657 8663 8669 8675 Dysprosium Dy 66 162.50 Rubidium Rb 37 85.47

74
8681 8686 1 1 2 2 3 4 4 5 5
Einsteinium Es 99 — Ruthenium Ru 44 101.07
8692 8698 8704 8710 8716 8722 8727 8733 8739 8745 1 1 2 2 3 4 4 5 5 Erbium Er 68 167.26 Samarium Sm 62 150.35
75 8751 8756 8762 8768 8774 8779 8785 8791 8802 Europium Eu 63 151.96 Scandium Sc 21 44.956
76 8808 8814 8820 8825 8831 8837 8842 8848
8797
8854 8859
1
1
1
1
2
2
2
2
3
3
3
3
4
4
5
5
5
5
Fcrmium Fm 100 — Selenium Se 34 78.96
Fluorine F 9 18.9984 Silicon Si 14 28.086 ± 0.001
77 8865 8871 8876 8882 8887 8893 8899 8904 8910 891S 1 1 2 2 3 3 4 4 5 Francium Fr 87 — Silver Ag 47 107.870*
78 8921 8927 8932 8938 8943 8949 8954 8960 8965 8971 1 1 2 2 3 3 4 4 5
Gadolinium Gd 64 157.25 Sodium Na 11 22.9898
79 8976 8982 8987 8993 8998 9004 9009 9015 9020 9025 1 I 2 2 3 3 4 4 5
Gallium Ga 31 69.72 Strontium Si 38 87.62
Germanium Gc 32 72.59 Sulphur s 16 32.064 ± 0.003
80 9031 9036 9042 9047 9053 9058 9063 9069 9074 9079 1 1 2 2 3 3 4 4 5
Gold Au 79 196.967 Tantalum Ta 73 180.948
Hafnium Hf 72 178.49 Technetium Tc 43
81 9085 9090 9096 9101 9106 9112 9117 9122 9128 9133 2 2 Helium He 2 4.0026 Tellurium Te 52 127.60
1 1 3 3 4 4 5
82 9138 9143 9149 9154 9159 9165 9170 9175 9180 9186 1 1 2 2 3 3 4 4 5
Holmium Ho 67 164.930 Terbium Tb 65 158.924
83 9191 9196 920L 9206 9212 9217 9222 9227 9232 9238 1 1 2 2 3 3 4 4 5
Hydrogen H 1 1.00797 ±0.00001 Thallium Tl 81 204.37
Indium In 49 114.82 Thorium Th 90 232.038
84 9243 9248 9253 9258 9263 9269 9274 9279 9284 9289 1 1 2 2 3 3 4 4 5
Iodine I 53 126.9044 Thulium Tm 69 168.934
85 9294 9299 9304 9309 9315 9320 9325 9330 9335 9340 2 2 Iridium lr 77 192.2 Tin Sn 50 118.69
1 1 3 3 4 4 5
86 9345 9350 9355 9360 9365 9370 9375 9380 Iron Fc 26 55.847 • Titanium Ti 22 47.90
9385 9390 1 1 a 2 3 3 4 4 5 Krypton Kr 36 83.80 Tungsten W 74 183.85
87 9395 9400 9405 9410 9415 9420 9425 9430 9435 9440 1 i 2 2 3 3 4 4
Lanthanum La 57 138.91 Uranium U 92 238.03
88 9445 9450 9455 9460 9465 9469 9474 9479 9484 9489 1 i 2 2 3 3 4 4
Lead Pb 82 207.19 Vanadium V 23 50.942
89 9494 9499 9504 9509 9513 9518 9523 9528 9533 9538
Lithium Li 3 6.939 Xenon Xe 54 131.30
1 i 2 2 3 3 4 4 Lutetium Lu 71 174.97 Ytterbium Yb 70 173.04
90 9542 9547 9552 9557 9562 9566 9571 9576 9581 9586 I i 2 2 3 3 4 4
Magnesium Mg 12 24.312 Yttrium Y 39 88.905
Manganese Mn 25 54.9380 Zinc Zn 30 65.37
91 9590 9595 9600 9605 9609 9614 9619 9624 9628 9633 1 i 2 2 3 3 4 4
Mcndclcvium Md 101 — Zirconium Zr 40 91.22
92 9638 9643 9647 9652 9657 9661 9666 9671 9675 9680 1 i 2 2 3 3 4 4 •Atomic weights so designated arc known
93 9685 9689 9694 9699 9703 9708 9713 9717 9722 9727 1
1 i 2 2 3 3 4 4 composition. Ine observed ranges are:
94 9731 9736 9741 9745 9750 9754 9759 9763 9768 9773 Hydrogen ±0.00001 Oxygen
1 i 2 2 3 3 4 4 ±0.0001
95 9777 9782 9786 9791 9795 9800 9805 9809 9814 9818 Boron ±0.003 Silicon ±0.001
1 i 2 2 3 3 4 4
96 9823 9827 9832 9836 9841 9845 9850 9854 9859 9863 1 i 2 2 3 3 4 4
Carbon ±0.00005 Sulphur ±0.003
97 9868 9872 9877 9881 9886 9890
Atomic weights so designated arc believed to have the following experimental uncertainties:
9894 9899 9903 9908 1 i 2 2 3 3 4 4
98 9912 9917 9921 9926 9930 9934 9939 9943 9948 9952 Chlorine ±0.001 Bromine ±0.002
1 i 2 2 3 3 4 4 Chromium ±0.001 Silver
99 9956 9961 9965 9969 9974 9978 9983 99S7 9991 9996 2 2
±0.003
1 3 3 3 4 Iron ±0.003
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9 For other elements the last digit is believed to be reliable to ±0.5.
(Table reproduced from I.U.P.A.C. Bulletin number 14B, with permission from Bulterworths
Scientific Publications, Publishers to the International Union of Pure and Applied Chemistry.]
^

Index

ACETALDEHYDE, 336 radical test, 517

Acetic acid, 338 salts, preparation, 234
Acetyl chloride, 340 properties, 433
Acetylene, 330 sulphate, 291, 417
molecule shape, 76 sulphide, 399
Acid radicals, tests, 515 Amphoteric hydroxide, 259
salt,227 Amylopectin, 188
Acids, 222 A my lose. 188
Air, 171, 178 Analysis, 26
Alcohols, 333 Anhydride, 407
Aldehyde, 336 Aniline, 323
Alkalis, 226 Anode, 139
Alkanes, 319 Antifreeze, 328
structure, 321 Aragonitc, 475
Alkencs, 326 Argon, 66, 177
Alkyncs, 330 Artificial elements, 505

Allotropy, 287 Aston, 38

carbon, 287 Atom, 19, 65
oxygen, 285 Atomic fission, 503
phosphorus, 456 fusion, 505
sulphur, 392 number, 66, 78
Alpha-particle scatter, 63 pile, 504
Alpha-rays, 498 structure, 62
Aluminium, 477 theory, 14
carbide, 199 modernised, 91
chloride, 370 weight, 34, 38, 103
hydroxide, 251 Atomic weight scale (1962), 103
oxide, 242 Atomicity, 19, 100
sulphate, 416 Avogadro constant, 107
Alums, 417 number, 107
Amines, 343
Aminoacetic acid, 340 Baking powder, 317
Ammonal, 441 Barium chloride, 233, 219
Ammonia, 426 sulphate, 233
formula, 113 Base, 224
molecule shape, 74 Basic oxide, 242
Ammonium carbonate, 309 radical tests, 516
chloride, 370 salt, 228
hydroxide, 430 Basicity, 228
ion, 70 Bccquerel, 498
nitrate, 441 Benzene, 323
nitrite, 424 Bessemer Process (steel), 486
radical, 431, 517 Beta-rays, 499
537
538 INDEX INDEX 539

Bicarbonatcs, see hydrogen carbonates Caustic potash, 252, soda, 253 Dative covalency, 69 Fatty 338
acids,
Black copper oxide, 28, 247 CelL Leclanche, 152 Decomposition, 153 Fermentation, 333
Blast furnace, 484 Cement, 258 Definitions, 524 Ferric, see iron(HI)
Bleaching, 358, 406 Chalk, 314 Degradation, 334 Ferrous, see ironfjl)
powder, 364 Chamber Process (H.SOJ, 411 Deliquescence, 256, 371, 524 Fixation of nitrogen, 452
Boiling-point, 83, 191 Charles's Law, 42, 79 MI, 166 Flame, 303
Bomb, atomic, 503 Chemical change, 2 Detergent, 203 Flame test, 374
hydrogen, 505 equilibrium, 156 Diamond, 288 Formic acid, 338
Boyle's Law, 41, 79 solution, 210 Diastase, 333 Formula;, 20, 90
Brass, 495 Chloride radical, test, 515 Diethyl ether, 336 empirical, 108
Bromide radical test, 516 Chlorides, 369 Diffusion, 268 experiments on, 45
Bromine, 376 Chlorine, 355, molecule, 375 Dinitrogcn oxide, 445 gases, 112
in periodicity, 85 water, 359 formula, 118 molecular, 108
Bronze, 495 Chloroacctic acids, 340 Displacement, 154 structural, 321, 325
Brownian movement, 13, 82 Chloroform, 321, 298 Dissociation, 159 Fountain experiment, 428
Burette and pipette, 126 Chlorophyll, 186 Distillation, 191 Frasch, 389
Butane, 322, 325 Chromatography, 341 fractional, 218 Freezing-point, 217
Coal fire, reactions, 302 Double decomposition, 160, 232 Fuel gas (petroleum), 292
Calamine, 480 Coal-gas, 290 Dutch metal, 362 Fuel oil, 324
Calcite,475 Coinage metals, 495 Furring, 204
Calcium, 476 Combination, 153 Efflorbscbnce, 313, 525
bicarbonate, 317 Combustion, 171, 303 Einstein equation, 25, 502 Galena, 491
carbide, 461 in chlorine, 360, 361 Electrochemical series, 133 Galvanic couple, 151
carbonate, 314 of air, 303 Electrodes, 139 Galvanisation, 483
chloride, 178, 371 Common salt, 370 Electrolysis, 137 Gamma-rays, 499, 507
hydrogen carbonate, 317 Compounds, 7 Electrolyte, 139 Gas oil, 324
hydroxide, 258 Contact process, H.SOJ, 412, 157 Electron, 62, 64, 498 Gas preps, revision, 521
nitrate,443 Co-ordinate valency, 69 in atoms, 64 Gay-Lussac's Law, 95, 98
oxide, 243 Copper, 493 Electrothermal reactions, 461 German silver, 446
sulphate, 418 Copper(l) acetylide, 332 Electrovalency, 66 Glass, 352
sulphide, 401 chloride, 248 Element, 6 Glucose, 187, 334
Calculations, gas vol., 41, 105 oxide, 28, 248 Elements, table of, 532, 535 Glycine, 340
weights, 54 Copper(li) carbonate, 315 Endothermic reaction, 166 Glycol (ethylene), 328
Calor gas, 322 hydroxide, 260 Equations, 22 Gossage, 254
Calorie, 166 nitrate, 26, 443 Equivalent, 36, 45 Gram-atom, 39
Candle, combustion of, 180 oxide, 26, 247 experimental, 45-51 Gram-molecule, 104
Carbon, 287 pyrites, 493 of a compound, 129 Gram-molecular volume, 104
atomic weight, 109 sulphate, 231, 420 Ester, 340, 337 weight, 104
atomic weight scale, 103 sulphide, 402 Ethane, 321 Graphite, 288
Carbon dioxide, 294 Covalency, 68 Ethanol, 333 Gunpowder, 442
formula, 119 Cracking (petroleum), 324 Ethene, 326
in life processes, 185 Crystallisation, 230 Ethyl acetate, 337 Haber's Process, 431
Carbon disulphide, 8, 291, 297 water of, 208, 219 alcohol, 333 Hxmatite, 483
Carbon monoxide, 298 Crystal structure, diamond, 288 chloride, 335 Half-life, 501
formula, 121 graphite, 288 hydrogen sulphate, 328, 327 Halogens compared, 85, 385
Carbon tetrachloride, 297, 353, 321 iodine, 75 iodide, 328 Hardness of water, 201
Carbonate radical, test, 516 sodium chloride, 371 Ethylene, 326 Heat of combustion, 166
Carbonates, 309, 233 Cupric, see copperf.Ii) dichloride, 327 of neutralisation, 167
Carboxyl group, 338 Cuprous, see copper(I) glycol, 328 constant, 226
Carnallite, 376 Curie, Marie, 498 molecule shape, 76 of precipitation, 168
Cast iron, 485 Cyclic compounds, 323 polymerisation, 329 of solution, 167
155,273
Catalysis, Exothermic reaction, 165 Helium, 177, 84, 499
Cathode, 139 Dalton 12 Explosion, 308 Homologous series, 322
 1

540 INDEX INDEX 541

Hydriodic acid, 383 of hydrogen, 268 from 277
liquid air,
Macromolecule, 288, 187
Hydrobromic acid, 379 of lead, 492 426 84
in periodicity,
Magnesium, 46, 172, 197, 296,
Hydrocarbons, 319 Nitrogen dioxide, 449
extraction, 496
Hydrochloric acid, 366 Joule, 166 Nitrogen monoxide, 447, 49
oxide, 172, 277
Hydrogen, 263 formula, 116
sulphate, 230
atomicity, 99 kcal, 166 Nitrous oxide, sec dinitrogen oxide
Magnetite, 246
bromide, 379 kJ, 166 Non-metals, 275, 466, 469
Malt, 333
carbonates, 316 Kekule, 323 Normal solution, 129
Maltase, 334
chloride, 366 Kerosene, 324 N.T.P., 43
Maltose. 333
formula, 1 12, in toluene, 240 Kinetic theory, 79 Nuclear energy, 502
Manganese dioxide, see next entry
iodide, 383 gases, 79 Nylon, 344
Manganese(IV) oxide, 273, 355
nascent, 267, 490 liquids, 81
Marble, 314
peroxide, 280 solids, 79 Olefines, 326
Margarine, 264, 328
sulphide, 395 Krypton, 177 Mass number, 78, 500 Ores, 479
formula, 118 Oxalic acid, 299, 415, 339
Mass spectrometer, 38
Hydrogen ion index, 237 Lacq (sulphur), 390
Match industry, 457 Oxidation, 161
Hydrolysis, 372, 525 Lampblack, 288 Melting-point, 81,217 Oxides, 242, 407
of ester, 337 Law, Boyle's, 41 Mercury, 248, 253 classified, 278
Hydroxide, basic, 225 Charles's, 42 Oxygen, 174, 178, 272
Mercury (II) oxide, 248
Hydroxides, 251 combining volumes, 95 from liquid air, 277
Metals. 80, 72, 133, 463
Hydroxyl group reactions, 335, conservation of energy, 168 Metallic bond, 72 Ozone, 283
340 conservation of mass, 24 molecular formula of, 120
Methane, 320
Hypochlorites, 364 constant composition, 26 molecular shape, 75
Hypothesis, 13 definite proportions, 26 Paraffins,319
Methyl alcohol (methanol), 333, 294
Faraday's, 150 chloride, 335 structure, 321
Iceland spar, 475 Gay-Lussac's, 95, 98
group, 321 Pentane, 320
Indicator, 127, 239 multiple proportions, 28 Peptide linkage, 341, 345
methacrylatc polymer, 346
universal, 239 partial pressures, 44, 79 Periodicity, 83
Mcthylamine, 343
Iodide radical test, 516 reciprocal proportions, 30 Permutit process, 208
Mixtures, 5, 7, 180
Iodides, 384 Law-Theory relation, 30
Molar solution, 123 Peroxides, 248, 280, 518
Iodine, 381 L-D process (steel), 486 Molar volume (gases), 105 Pcrspex, 346
crystal,75 Le Chatelier's Principle, 156, 431
Mole, 39. 107, 525 Petrol, 324
molecule, 75 Lead dioxide, see lcad(iV) oxide Petroleum, 324
Molecular weight, 35, 54, 99, 102
in periodicity, 85 Lead, 491, accumulator, 189 fuel gas, 292
Molecules, 19, 99
Ionic theory, 139 chamber process, 41 pH, 237
shapes of, 73
Iron, 483 isotopy, 77 Phenol, 323, 291
Monochloroacetic acid, 340
passive, 488 Lead(ll) carbonate, 315 Phosphine, 458
Mortar, 258
pyrites, 411,419 chloride. 373 Phosphorus, 175, 176, 276, 455
Mother of vinegar, 339
rusting of, 182 hydroxide, 260 acids of, 459
Mycoderma aceli, 339
Iron(II) chloride, 372, 489 nitrate,443 allotropy, 456
compounds, 489, 517 oxide, 247 460
Naphtha, 292, 324 fertiliser,
hydroxide, 259 sulphate, 232, 416 oxychloride, 71
Nascent hydrogen, 490
oxide, 489 sulphide, 402, 399 pentachloride, 459, 335, 340
Natural gas, 321
sulphate, 419 Lead(IV) oxide, 249 pentoxide, 459
Neon, 84, 177
sulphide, 9, 402 Lime, 243, 198 periodicity of, 84, 87
Neutralisation, 225, 233
Iron(IH) chloride, 362, 489 Limestone, 314 340
Neutron, 63, 77 trichloride, 458, 335,
compounds, 489 Lime-water, 258 trioxide, 459
Nickel catalyst, 328, 331
hydroxide, 260, 489 Liquefaction, SO,, 407 Photocatalysis, 155, 321, 340
Nitrates, 234, 440
oxide, 246 N.O., 449 Photoelectric effect, 373
Nitric acid, 435, 164
sulphate, 420, 489 general, 81
Nitric oxide, sec nitrogen monoxide Photosynthesis, 186
Isomerism, 324 Lithium, flame 374
test,
Nitrogen, 174, 178 Physical change, 2
Isotopy, 77 in periodicity, 84 cycle, 452 Pig iron, 485
of chlorine, 77 Litmus, 233 Pitchblende, 498
fixation, 452
 ^
542 INDEX INDEX 543

Plaster of Paris, 418 Sabatier's reaction, 328 Steel, 486 Universal indicator, 237, 239
Platinised asbestos, 410 Sal-ammoniac, 370 Stellar energy, 504 Unsaturation, ethylene, 327, 329
Polyester, 337 Salts, 227 S.t.p.,43 acetylene, 331
Polymerisation, 329, 332, 345, 346 acid, 227 Strontium-90, 507 Uranium-235, 503
Polystyrene, 345 basic, 228 Styrene, 345 Uranium-238, 501
Polythene, 329 methods of preparation, 229 Sublimation, 81, 433
Polyvinyl chloride, 461 normal, 227 Sulphates, 416 Valency, 36, 66, 84, 90
Potassium, 195, 471 Saturated compounds, 329 Sulphides, 401 van der Waals forces, 69

bromide, 377, 516 solution, 21 Sulphur, 7, 276, 289, 389 Vapour density, 100
carbonate, 309 Scheele, 272, 355 allotropcs, 392 Vinyl chloride, 461
chlorate, 272, 364 Sea water, 201 dioxide, 403 Voltaic couple, 151
chloride, 370 Side chain, 324 formula, 120
dichromate, 405 Silica, 349 trioxide, 199, 410 Water, 190, 270
hydroxide, 195, 234, 252, 471 Silica garden, 351 Sulphuric acid, 411,438 composition of, 1 15, 200
iodide, 364, 381, 516 Silica gel, 351 Sulphurous acid, 363, 407 -gas, 294
nitrate, 234, 441 Silicon, 348 Supersaturation, 215 hardness of, 201
oxide, 198, 243 in periodicity, 87 Suspensions, 210 of crystallisation, 208, 219
periodicity of, 84 tetrachloride, 353 tests, 270
Symbols, 17
permanganate, 192, 275, 356, Silver acetylide, 332 Dalton, 22 Water-glass, 351
405 chloride, 373 Synthesis, 269, 337 Weights, calcs. involving, 54
sulphate, 234, 418 nitrate, 444, 515 White 315
lead,
sulphide, 400 Smokeless fuel, 292 Tartaric acid, 339 Wood 333
spirit,

Pressure effects, 40, 157, 431 Soap, 202 Temperature effects, 42, 154, 432, 213 Wrought iron, 486
Priestley, 272 Sodium, 196. 471 Tempering (steel), 487
Producer gas, 293 carbonate, 206, 310 Tcrylene, 337 Zinc, 50, 482
Propane, 321 chloride, 148, 370 Tetrammine copper(ir) ion, 71 carbonate, 314, 480
Protein, 340 ethoxide, 335 Thermal dissociation, 159, 450 hydroxide, 259
Proton, 63, 66, 78 hydrogen carbonate, 316 Thermit, 479 nitrate, 444
Puddling (iron), 486 hydrogen sulphate, 227, 412 Titrations, 126 oxide, 245
PVC (polyvinyl chloride), 461 hydroxide, 147, 233, 253 Transmutation (elements), 501 sulphate, 230, 419
Pyrene, 298 methoxide, 335 Tri-iron tetroxide, 266, 277 sulphide, 401, 399, 480
nitrate, 234, 442 Trilead tetroxide, see red lead white, 245
Quartz, 348 nitrite, 424, 442 Turpentine, 360 Zymase, 334
Quicklime, 243 oxide, 243
in periodicity, 84, 87
Radical, 515-7
tests, peroxide, 248
Radioactivity, 498 radio, 506, 507
kinds of, 500 351
silicate,
Radio-carbon, 507 sulphate, 233, 418
Radio-cobalt, 507 sulphide, 400
Radio-iodine, 507 sulphite, 409
Radio-phosphorus, 506 Solution, 194, 209, 430
Radio-sodium, 506, 507 Solvay Process, 310
Radio isotopes, 506 Spring water, 201, 190
Radon, 499 Stalactites, stalagmites, 204
Rainwater, 190, 201 Starch, 186
Rare gases, 177, 424 formula, 187
Red lead, 249 hydrolysis, 187
Reduction, 161 molecule, 187
Respiration, 185 test, 188
Reversible reactions, 154 Steam, 197, 265, 294
River water, 190, 201 formula of, 116
Rusting, 182, 483 molecule shape, 74
oo>
Sftfe