Service chemistry : being a short manual of chemistry and metallurgy and their application in the naval and military services

Preface

At no time in the world’s history has the need for scientific knowledge in our two great Services been more important than at the present, whilst probably at no time has the period which could be devoted to acquiring it been shorter ; and this book is an attempt to supply, as far as may be, a rational treatise on the more chemical side of the many subjects with which Officers are brought in almost daily contact.

In the short time that can be devoted to subjects outside the professional Service routine, it is impossible to acquire a complete knowledge of any of the many branches of science that enter into modern Service work, but the authors have found from long experience that it is quite possible to so develop the purely theoretical side of a science as to lead naturally up to the more technical details of such Service questions as are necessary to a Naval or Military career.

The technical side of a science is merely its adaptation to our special needs, and without a knowledge of the facts and laws that govern the results we desire to attain, a Service technology would be a mere collection of data, useless in the future and of but little present value. On the other hand, to attempt to educate a busy Officer of any branch in all the modern theories, before he had grasped the importance to him of their application, would be to court failure, and we have attempted so to formulate the fundamental facts and theories of modern chemistry as to form a firm foundation for their application to such questions as modern explosives, fuel problems, the physical and chemical characteristics of the metals and alloys, military ballooning, boiler incrustations.

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Prejace corrosion, protective paints, anti-fouling compositions, and the host of other subjects on which knowledge is necessary to ensure progress, and whicli are dealt mth as the scientific side of the book leads up to them. ^

The fact that this is the fourth edition of the book shows that it lias been acceptable to many, and in order to keep up with the rapid advances made in science during the last few years, it has been largely re-written to bring it up-to-date, and embraces much material, not available in the ordinary text-books, of importance to engineers and others. The authors, therefore, hope it may appeal to an even larger circle of readers than the Service students for whom it was specially prepared.

V. B. L.

J. S. S. B.

Eoyal Naval College, Greenwich,

Chapter I Introductory

PAGE

Physical and chemical change — Conservation of matter and energy — Elements — Mechanical mixtures and chemical compounds — Analysis and synthesis — The three states of matter — Liquefaction of gases — Refrigeration ........... 1

Chapter II Theoretical

Law of constant proportion — Law of multiple proportion — The atomic theory — Law of gaseous volumes — Complex nature of gaseous molecules — Influence of temperature and pressure on gases — The kinetic theory — Atomic and molecular weight — Atomic and molecular weights from density — Atomic weight of non-volatile elements — Determination of molecular weight hy other methods — Equivalents and atomic weights — Valency or atomicity — Symbols and formula — Equations — Reversible reactions and equilibrium — Empirical and molecular formulte — Graphic and constitutional formulas — Thermo-chemistry ... 14

Chapter III

Preparation — Properties — Weight — Effect upon sound — Solubility — Diffusion of gases— Military ballooning — Chemical behaviour of hydrogen 37

Chapter IV Che3iistry Op The Galvanic Battery

Heat of chemical action converted into galvanic electricity — “ Polarisation ” — Arrangements adopted in various cells — Chemical actions taking place in the “ Daniell ” — “ Varley-Daniell ” — “ Menotti-Daniell ” —

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PAG K

“ Leclancli6 ” — “ Grove ” — “ Bunseu ” — “ Bichromate ” — Secondary cells — The Edison cell — Electrolysis — Electrolites — ’The commercial production of hydrogen and oxygen hy electrolysis — Electro-metallurgy — Importance of the electro-chemical relations between metals on ships’ bottoms — Muntz metal — Zinc protectors — Zinc sheathing — Mooring vessels ............

Chapter V

Occurrence — Preparation of oxygen gas — Oxygen obtained from air — •

Properties of oxygen — Combustion in oxygen — Ozone . . . . G1

Chapter VI Oxides And Salts

Oxides, acid-forming, basic, and neutral — Salts — Formation — Normal, acid, and basic salts — Decomposition of salts — Nomenclature — Classification of the elements — The periodic system ...... G8

CHAPTER Vll

COMIU'STION

The Phlogistic theory — Lavoisier shows combustion to be active chemical combination — Reciprocal combustion — Slow combustion — Decay — Respiration — Spontaneous combustion — Point of ignition — Spontaneous ignition of charcoal, coal, oily rags, hay, etc. — Combustion by combined oxygen

CHART VIII

tVATEK AND ITS I'KOPERTIES

M ater — Composition of water by volume and weight — Physical properties of water — -Liitcnt heat — Specific heat — Change of volume during change of state — Boiling point of wnter — Spheroidal state — Solution — Water of crystallisation — Water of hydration — Circulation of w'atcr in Nature 94

CH.VPTER IX

THE IMPURITIES IN WATER

T’he natural impurities in rain, surface, spring, river and sea W'ator — Plardness in wntcr — Temporary hardness — Permanent hardness — The economic aspect of hard water— Natural impurities and their effect

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PAGE

upon health — Sewage contamination — Sources of drinking water — Purification of water — Filtration on the largo scale — Porter-Clark process — Pasteur-Chamherland filters — Ready methods for the purification of water ............ 112

CHAPTER X

BOILER INCRUSTATIONS

Saline constituents of fresh and sea water — Incrustations from different kinds of water — Causes of boiler incrustation — Calcium carbonate — Calcium sulphate — Solubility — Effect of concentration on sea water — Effect of temperature and pressure on the saline constituents of sea water — Formation of magnesium hydroxide in marine boiler deposits — Action of distilled water on boilers — Waste of fuel entailed by boiler incrustation — Prevention of incrustation — Anti-incrustators — Chemical and mechanical action of anti-incrustators — Zinc protectors in boilers —

Feed water heaters — Oily deposits ....... 123

CHAPTER XI

CARBON AND SOME OF ITS COMPOUNDS WITH HYDROGEN

Allotropic modifications of carbon — Diamond — Graphite — Carbon from organic sources — Absorbent properties of charcoal — General properties of carbon— Methane or marsh gas — Preparation and properties — Natural sources — Liberation of marsh gas in mines and coal bunkers — Fire-damp — Safety lamps— Ethylene or olefiant gas — Preparation — • Acetylene — Benzene — Isomerism — Coal gas and its manufacture — Structure of flame — Burners for gas — Illuminating power of gas . . 135

CHAPTER XII

THE OXIDES OF CARBON

Carbon dioxide — Preparation and properties — Solubility — Aerated waters — Liquefaction of carbon dioxide — Critical temperature — Composition of carbon dioxide — Carbon monoxide — Preparation and properties . .157

CHAPTER XIII

FUEL

The storage of energy in the growth of vegetation — Thermal values — The Calorie — The British Thermal Unit — The calculation of the thermal value of fuels — The direct determination of calorific values — Calorimeters— Calorific intensity —Solid fuels— Wood — Factors affecting its value as a fuel — Wood charcoal — Peat — Coal — The formation and

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I’AdlC

classification of coals— Coke — Liquid fuel — Petroleum — Its formation and composition — Liquid fuel burners — The methods of using liquid fuel — The value of liquid fuels for steam raising — Liquid fuel in the internal combustion engine — Petrol — Benzene — Alcohol — Heavy oil engines — Gaseous fuel — Natural gas— Coal gas — Coke oven gas — Water gas — Producer gas — Semi-water gas — Suction gas plant .... 166

CHAPTJ® XIV

XITllOGEN AND ITS COMPOUNDS

Nitrogen, occurrence in Nature — Preparation — Properties of nitrogen — Ammonia — Pormation in Nature — Preparation and properties of the gas— Liquid ammonia — Decomposition of ammonia — Ammonium salts — Ammonium amalgam — The oxides of nitrogen — Preparation and properties of nitrogen monoxide, dioxide, trioxide, tetroxide, pentoxide — Nitric acid — Oxidising action of nitric acid — Nitrates — Nitre for gunpowder— Formation of nitrates from the air — Tests for nitrogen . . 204

CHAPTEE XV

THE ATAIOSPHERE AND VENTILATION

The extent of the atmosphere — Weight of the atmosphere — The barometer — Composition of the atmosphere — Air a mechanical mixture and not a chemical compound — Gases other than oxygen and nitrogen present in the atmosphere — Argon, ammonia, water vapour, carbon dioxide — The natural actions which keep the composition of the atmosphere constant —Solid, liquid, and gaseous impurities present in the atmosphere — Ventilation — Ventilation of ships ....... 219

CIIAPTEP. XVI

EXPLOSIVES GUNPONVDEK

Nature and causes of explosion — Exothermic and endothermic compounds Glassification of explosives — Gunpowder — Ingredients and composition History of gunpowder — Pebble and prism powder — S.B.C. and E.X.E. powder — Built up charges — llequircments of a good cannon powder ElTcct of the prismatic form on the rate of burning of powder ^ Saltpetre — Purification — Chemical decompositions of saltpetre — Charcoal for gunpowder — Sulphur — Manufacture of gunpowder — iVlixing, milling, breaking down, pressing, granulating, dusting, glazing, stoving, finishing, and blending — jMeasurement of the pressure during firing powder — Crusher gauge — IMuzzle velocity — Bouleng6 chronograph Chemical changes taking place during the combustion of gunpowder —Gaseous and solid products formed— IMethod of calculating volume of gases produced and pressure exei-tcd .....

XI

CHAPTEE XVII

EXPLOSIVES — GUN-COTTON AND NITRO-GLYCERIN

PAGE

History — Action of nitric acid upon organic compounds — Cellulose — Collodion cotton — Gun-cotton — Gun-cotton an explosive compound and not an explosive mixture — IManufacture of Service gun-cotton — Precautions to be taken during manufacture — Testing finished gun-cotton— Properties — Explosion of gun-cotton by detonation — Theories of detonation — Wet gun-cotton — Storage-Products of combustion of gun-cotton — Force of fired gun-cotton — Nitro-giycerin — Manufacture of nitro-glycerin — Properties and decomposition — The downward action of high explosives .......... 252

CHAPTER XVIII

SMOKELESS POWDERS

Necessity for smokeless powders for Service purposes — Amide powders — Attempts to use gun-cotton — Schultze and E.C. powders — The modern smokeless Service powders — Cordite Mark I — The erosion of guns—

M.D. Cordite — Tubular Cordite — Stability tests — Pyro-cellulose — The foreign smokeless powders — Picric acid and the picrates — Lyddite — • Trinitro-cresol — Trinitro-toluene . . . . . . .275

CHAPTER XIX

BLASTING EXPLOSIVES AND FULMINATES

Requirements in blasting explosives — History — Blasting gunpowder — Sprengel explosives — Roburite — Bobbinite — Nitro-glycerin explosives ; Dynamite — Lithofracteur — Carbonite — Blasting gelatine — Factors of safety required in blasting explosives — Safety from accidental explosion — Safety during explosion — Noxious fumes from blasting explosives — Permitted explosives — The fulminates — Mercmdc fulminate — Detonators, etc. ............ 303

CHAPTER XX

SULPHUR AND SULPHUR COMPOUNDS

Sulphur — Occurrence in Nature — Preparation and properties — Sulphuretted hydrogen— Preparation and properties — Combustion of sulphuretted hydrogen — Use of the compound in analysis — Preparation and properties of sulphur dioxide — Action on vegetation and life — Sulphurous acid and the sulphites — Oxidation of sulphur dioxide — Sulphur trioxide — Sulphuric acid — Manufacture of oil of vitriol — Chamber crystals — Chamber acid — Concentration of sulphuric acid — Properties and composition of sulphuric acid — The sulphates ..... 319

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CHAPTER XXI

THE HALOGENS

PAGE

The Halogen elements — Chlorine — Preparation of the gas — Deacon’s process — Properties of chlorine — Bleaching action dependent on moisture — Hydrochloric acid gas— Preparation and properties — Effect of hydrochloric acid gas on vegetation — Chlorides — Chlorine monoxide — Hypochlorous acid — Bleaching powder — Hypochlorites and chlorates — Potassium chlorate — Percussion caps — Friction tubes — Coloured fires — Bromine and iodine — Preparation and properties — Bromides and iodides — Fluorine — Isolation of fiuorine — Fluor-spar — Hydrofluoric acid —Etching on glass ......... 333

CHAPTER XXII

SILICON AND ITS COMPOUNDS

Silicon — Silicon hydride — Silica or silicon dioxide — Occurrence and importance in Nature — Silicic acid — Dialysis — Silicates — Glass — Composition of glass — Manufacture of glass — Silicate of alumina — Clay — Pottery — Porcelain — Stoneware — Bricks — Building stones — Decay of building stones — Granites — Sandstones — Limestones — Dolomite — IMortar — Cements — Silicon tetrafluoride — Hydrofluosilicic acid — Boron . . 348

CHAPTER XXIII

PHOSPHOKUS AND ARSENIC

Extraction of phosphorus from bones and mineral phosphates — Properties of phosphorus — Red phosphorus — Matches — Wax vestas — Safety matches — Phosphuretted hydrogen or phosphine — Calcium phosphide — Holmes’ lights — Phosphorus trioxide — Phosphorus pentoxide — Metaphosphoric, pyrophosphoric, and orthophosphoric acid — Arsenic — Oxides of arsenic— Arseniuretted hydrogen— Marsh’s test — Testing for arsenic — Reinsch’s test ......... 359

CHAPTER XXIV

THE METALS

IMetallic properties — Occurrence of metals in Nature — Processes by which the common metals are obtained from their ores — General properties of the metals : lustre, colour, tensile strength, elasticity, malleabilitv,

ductility, specific gravity, conduction of heat and electricity, fusibility

Structure of metals : Fracture, micro-structure — The effect of heat and mechanical treatment on structure ....... 370

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CHAPTER XXV

IRON AND STEEL

I’AGE

Ores of iron— Production of iron in the blast furnace — Preparation of the ore, the furnace charge, construction of the furnace, working — Reactions in the furnace - Pig iron — Cast iron — Malleable castings — Wrought iron — The puddling process — Treatment of pnddled iron for production of bar iron — Steel — Cementation process — Crucible steel — Case hardening . 380

CHAPTER XXVI STEEL {continued)

The Bessemer process — Tropenas converter — Basic Bessemer process — Open Hearth steel, acid and basic — Comparison of the steel from different processes — Electric steel refining — Defects in steel ; blowholes, piping, segregation— Working of steel— Properties of iron and steel — Effect of other elements on properties — Alloy steels : manganese, nickel, chromium, silicon, tungsten, vanadium — Self-hardening steels — The heat treatment of steel ; hardening, tempering, and annealing — Manufacture of armour plate and gun forgings — Compounds of iron . , 402

CHAPTER XXVII

Occurrence and ores of copper — Metallurgy of copper — The Welsh process — Production in the blast furnace — Bessemerising copper mattes — Extraction from spent pyrites — Commercial copper — Electrolytic refining — Properties of copper — Compounds of copper ..... 430

CHAPTER XXVIII

LEAD, TIN, ZINC, CADMIUM, AND MERCURY

Lead — Metallurgy — Softening crude lead — Properties of lead — Compounds of lead — White lead — Tin — Metallurgy — Properties of tin — Compounds of tin — Zinc — Metallurgy — Belgian process — Silesian process — Properties of zinc — Compounds of zinc — Cadmium — Mercury . . . 439

CHAPTER XXIX

ALUMINIUM, GOLD, SILVER, PLATINUM

Aluminium — Production in the electric furnace — Properties and compounds — Gold— Parting of gold and silver— Silver — Cupellation — Properties and compounds — Photography: Wet process — Dry plate process— Development—Printing — Toning— Platinotype, ferrotype and carbon processes — Platinum ........... 453

XIV

CHAPTER XXX

NICKEL, COBALT, MANGANESE, CHROMIUM, ANTIMONY, AND

I'AGi:

Nickel — Production and properties — Cobalt — Manganese — Chromium — Chromium salts and chromates — Antimony and its compounds — Bismuth — Bismuth compounds ...... . 466

CHAPTER XXXI

BIETALS OF THE ALKALINE EARTHS

Magnesium and its compounds — Calcium and its compounds — Barium — Strontium — The alkali metals— Potassium — Compounds of potassium — Sodium — Compounds of sodium — The spectroscope — Ammonium compounds ........... 474

CHAPTER XXXII

ALLOYS

Definition of alloys — Amalgams — Properties attained by alloying — Alethods of formation of alloys — Nature of alloys — Freezing-point curves — Nature of Binary alloys ; where no chemical compound is formed and where definite compounds arc formed— Cast iron and steel as alloys . 4SS

CHAPTER XXXm

COMMERCIAL ALLOYS

Copper alloys — Brass, Muntz inetal, Aluminium brass — Bronze, Manganese bronze, Silicon bronze, Aluminium bronze, Machine brasses —

Tin and lead alloys, solders, pewter — Anti-friction metals— Electrical resistance alloys 508

CHAPTER XXXIY

THE CORROSION OF BIETALS, PROTECTION FROBI CORROSION, FOULING OF SHIPS AND ITS PREVENTION, PIGBIENTS

The rusting of iron — Action of sea water on iron and steel— Relative corrosion of iron and steel — Corrosion and pitting in boilers — Corrosion of plate — Rust cones — Corrosion of copper and its alloys — Protection

XV of iron from corrosion — Galvanising — Tinning — Protective compositions— Corrosion and protection of interior plates — Fouling and its prevention — Copper sheathing — Anti-fouling compositions — Conditions of animal and vegetable life on a ship’s bottom — Action of metallic poisons — Properties necessary in a good anti-fouling composition — Pigments — Causes which affect colour — Whites: white lead, zinc white — Blacks — Beds: iron oxide, red lead, vermilion — Yellows — Greens: copper greens, chromium green, mixed greens — Blues : ultramarine, Prussian Blue, indigo — Kaw and burnt umber — Sepia — Effect of light on water-colour paintings ........ 520

Appendix . . .559

. 509

PLATES rtATE

HGUliE

BESCUII’TIOX

Quenched steel — martensite ....

• J J

Sulphur segregate in steel ....