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AN ELEMENTARY
STUDY OF CHEMISTRY
BY
WILLIAM McPHERSON, PH.D.
PROFESSOR OF CHEMISTRY, OHIO STATE UNIVERSITY
AND
WILLIAM EDWARDS HENDERSON, PH.D.
ASSOCIATE PROFESSOR OF CHEMISTRY, OHIO STATE UNIVERSITY
REVISED EDITION
GINN & COMPANY BOSTON * NEW YORK * CHICAGO * LONDON
COPYRIGHT, 1905, 1906, BY WILLIAM MCPHERSON AND WILLIAM E. HENDERSON
ALL RIGHTS RESERVED
The Athenaeum Press GINN & COMPANY * PROPRIETORS * BOSTON * U.S.A.
Transcriber's note:
For Text: A word surrounded by a cedilla such as this signifies that the word is bolded in the text. A word surrounded by underscores like this signifies the word is italics in the text. The italic and bold markup for single italized letters (such as variables in equations) and "foreign" abbreviations are deleted for easier reading.
For numbers and equations: Parentheses have been added to clarify fractions. Underscores before bracketed numbers in equations denote a subscript. Superscripts are designated with a caret and brackets, e.g. 11.1^{3} is 11.1 to the third power.
Appendix A and B have been moved to the end of the book. Minor typos have been corrected.
PREFACE
In offering this book to teachers of elementary chemistry the authors lay no claim to any great originality. It has been their aim to prepare a text-book constructed along lines which have become recognized as best suited to an elementary treatment of the subject. At the same time they have made a consistent effort to make the text clear in outline, simple in style and language, conservatively modern in point of view, and thoroughly teachable.
The question as to what shall be included in an elementary text on chemistry is perhaps the most perplexing one which an author must answer. While an enthusiastic chemist with a broad understanding of the science is very apt to go beyond the capacity of the elementary student, the authors of this text, after an experience of many years, cannot help believing that the tendency has been rather in the other direction. In many texts no mention at all is made of fundamental laws of chemical action because their complete presentation is quite beyond the comprehension of the student, whereas in many cases it is possible to present the essential features of these laws in a way that will be of real assistance in the understanding of the science. For example, it is a difficult matter to deduce the law of mass action in any very simple way; yet the elementary student can readily comprehend that reactions are reversible, and that the point of equilibrium depends upon, rather simple conditions. The authors believe that it is worth while to present such principles in even an elementary and partial manner because they are of great assistance to the general student, and because they make a foundation upon which the student who continues his studies to more advanced courses can securely build.
The authors have no apologies to make for the extent to which they have made use of the theory of electrolytic dissociation. It is inevitable that in any rapidly developing science there will be differences of opinion in regard to the value of certain theories. There can be no question, however, that the outline of the theory of dissociation here presented is in accord with the views of the very great majority of the chemists of the present time. Moreover, its introduction to the extent to which the authors have presented it simplifies rather than increases the difficulties with which the development of the principles of the science is attended.
The oxygen standard for atomic weights has been adopted throughout the text. The International Committee, to which is assigned the duty of yearly reporting a revised list of the atomic weights of the elements, has adopted this standard for their report, and there is no longer any authority for the older hydrogen standard. The authors do not believe that the adoption of the oxygen standard introduces any real difficulties in making perfectly clear the methods by which atomic weights are calculated.
The problems appended to the various chapters have been chosen with a view not only of fixing the principles developed in the text in the mind of the student, but also of enabling him to answer such questions as arise in his laboratory work. They are, therefore, more or less practical in character. It is not necessary that all of them should be solved, though with few exceptions the lists are not long. The answers to the questions are not directly given in the text as a rule, but can be inferred from the statements made. They therefore require independent thought on the part of the student.
With very few exceptions only such experiments are included in the text as cannot be easily carried out by the student. It is expected that these will be performed by the teacher at the lecture table. Directions for laboratory work by the student are published in a separate volume.
While the authors believe that the most important function of the elementary text is to develop the principles of the science, they recognize the importance of some discussion of the practical application of these principles to our everyday life. Considerable space is therefore devoted to this phase of chemistry. The teacher should supplement this discussion whenever possible by having the class visit different factories where chemical processes are employed.
Although this text is now for the first time offered to teachers of elementary chemistry, it has nevertheless been used by a number of teachers during the past three years. The present edition has been largely rewritten in the light of the criticisms offered, and we desire to express our thanks to the many teachers who have helped us in this respect, especially to Dr. William Lloyd Evans of this laboratory, a teacher of wide experience, for his continued interest and helpfulness. We also very cordially solicit correspondence with teachers who may find difficulties or inaccuracies in the text.
The authors wish to make acknowledgments for the photographs and engravings of eminent chemists from which the cuts included in the text were taken; to Messrs. Elliott and Fry, London, England, for that of Ramsay; to The Macmillan Company for those of Davy and Dalton, taken from the Century Science Series; to the L. E. Knott Apparatus Company, Boston, for that of Bunsen.
THE AUTHORS
OHIO STATE UNIVERSITY
COLUMBUS, OHIO
CONTENTS
CHAPTER PAGE I. INTRODUCTION 1
II. OXYGEN 13
III. HYDROGEN 28
IV. WATER AND HYDROGEN DIOXIDE 40
V. THE ATOMIC THEORY 59
VI. CHEMICAL EQUATIONS AND CALCULATIONS 68
VII. NITROGEN AND THE RARE ELEMENTS IN THE ATMOSPHERE 78
VIII. THE ATMOSPHERE 83
IX. SOLUTIONS 94
X. ACIDS, BASES, AND SALTS; NEUTRALIZATION 106
XI. VALENCE 116
XII. COMPOUNDS OF NITROGEN 122
XIII. REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIUM 137
XIV. SULPHUR AND ITS COMPOUNDS 143
XV. PERIODIC LAW 165
XVI. THE CHLORINE FAMILY 174
XVII. CARBON AND SOME OF ITS SIMPLER COMPOUNDS 196
XVIII. FLAMES,—ILLUMINANTS 213
XIX. MOLECULAR WEIGHTS, ATOMIC WEIGHTS, FORMULAS 223
XX. THE PHOSPHORUS FAMILY 238
XXI. SILICON, TITANIUM, BORON 257
XXII. THE METALS 267
XXIII. THE ALKALI METALS 274
XXIV. THE ALKALINE-EARTH FAMILY 300
XXV. THE MAGNESIUM FAMILY 316
XXVI. THE ALUMINIUM FAMILY 327
XXVII. THE IRON FAMILY 338
XXVIII. COPPER, MERCURY, AND SILVER 356
XXIX. TIN AND LEAD 370
XXX. MANGANESE AND CHROMIUM 379
XXXI. GOLD AND THE PLATINUM FAMILY 390
XXXII. SOME SIMPLE ORGANIC COMPOUNDS 397
INDEX 421
APPENDIX A Facing back cover
APPENDIX B Inside back cover
LIST OF FULL-PAGE ILLUSTRATIONS
PAGE ANTOINE LAURENT LAVOISIER Frontispiece
JOSEPH PRIESTLEY 14
JOHN DALTON 60
WILLIAM RAMSAY 82
DMITRI IVANOVITCH MENDELEEFF 166
HENRI MOISSAN 176
SIR HUMPHRY DAVY 276
ROBERT WILHELM BUNSEN 298
AN ELEMENTARY STUDY OF CHEMISTRY
CHAPTER I
INTRODUCTION
The natural sciences. Before we advance very far in the study of nature, it becomes evident that the one large study must be divided into a number of more limited ones for the convenience of the investigator as well as of the student. These more limited studies are called the natural sciences.
Since the study of nature is divided in this way for mere convenience, and not because there is any division in nature itself, it often happens that the different sciences are very intimately related, and a thorough knowledge of any one of them involves a considerable acquaintance with several others. Thus the botanist must know something about animals as well as about plants; the student of human physiology must know something about physics as well as about the parts of the body.
Intimate relation of chemistry and physics. Physics and chemistry are two sciences related in this close way, and it is not easy to make a precise distinction between them. In a general way it may be said that they are both concerned with inanimate matter rather than with living, and more particularly with the changes which such matter may be made to undergo. These changes must be considered more closely before a definition of the two sciences can be given.
Physical changes. One class of changes is not accompanied by an alteration in the composition of matter. When a lump of coal is broken the pieces do not differ from the original lump save in size. A rod of iron may be broken into pieces; it may be magnetized; it may be heated until it glows; it may be melted. In none of these changes has the composition of the iron been affected. The pieces of iron, the magnetized iron, the glowing iron, the melted iron, are just as truly iron as was the original rod. Sugar may be dissolved in water, but neither the sugar nor the water is changed in composition. The resulting liquid has the sweet taste of sugar; moreover the water may be evaporated by heating and the sugar recovered unchanged. Such changes are called physical changes.
DEFINITION: Physical changes are those which do not involve a change in the composition of the matter.
Chemical changes. Matter may undergo other changes in which its composition is altered. When a lump of coal is burned ashes and invisible gases are formed which are entirely different in composition and properties from the original coal. A rod of iron when exposed to moist air is gradually changed into rust, which is entirely different from the original iron. When sugar is heated a black substance is formed which is neither sweet nor soluble in water. Such changes are evidently quite different from the physical changes just described, for in them new substances are formed in place of the ones undergoing change. Changes of this kind are called chemical changes.
DEFINITION: Chemical changes are those which involve a change in the composition of the matter.
How to distinguish between physical and chemical changes. It is not always easy to tell to which class a given change belongs, and many cases will require careful thought on the part of the student. The test question in all cases is, Has the composition of the substance been changed? Usually this can be answered by a study of the properties of the substance before and after the change, since a change in composition is attended by a change in properties. In some cases, however, only a trained observer can decide the question.
Changes in physical state. One class of physical changes should be noted with especial care, since it is likely to prove misleading. It is a familiar fact that ice is changed into water, and water into steam, by heating. Here we have three different substances,—the solid ice, the liquid water, and the gaseous steam,—the properties of which differ widely. The chemist can readily show, however, that these three bodies have exactly the same composition, being composed of the same substances in the same proportion. Hence the change from one of these substances into another is a physical change. Many other substances may, under suitable conditions, be changed from solids into liquids, or from liquids into gases, without change in composition. Thus butter and wax will melt when heated; alcohol and gasoline will evaporate when exposed to the air. The three states—solid, liquid, and gas—are called the three physical states of matter.
Physical and chemical properties. Many properties of a substance can be noted without causing the substance to undergo chemical change, and are therefore called its physical properties. Among these are its physical state, color, odor, taste, size, shape, weight. Other properties are only discovered when the substance undergoes chemical change. These are called its chemical properties. Thus we find that coal burns in air, gunpowder explodes when ignited, milk sours when exposed to air.
Definition of physics and chemistry. It is now possible to make a general distinction between physics and chemistry.
DEFINITION: Physics is the science which deals with those changes in matter which do not involve a change in composition.
DEFINITION: Chemistry is the science which deals with those changes in matter which do involve a change in composition.
Two factors in all changes. In all the changes which matter can undergo, whether physical or chemical, two factors must be taken into account, namely, energy and matter.
Energy. It is a familiar fact that certain bodies have the power to do work. Thus water falling from a height upon a water wheel turns the wheel and in this way does the work of the mills. Magnetized iron attracts iron to itself and the motion of the iron as it moves towards the magnet can be made to do work. When coal is burned it causes the engine to move and transports the loaded cars from place to place. When a body has this power to do work it is said to possess energy.
Law of conservation of energy. Careful experiments have shown that when one body parts with its energy the energy is not destroyed but is transferred to another body or system of bodies. Just as energy cannot be destroyed, neither can it be created. If one body gains a certain amount of energy, some other body has lost an equivalent amount. These facts are summed up in the law of conservation of energy which may be stated thus: While energy can be changed from one form into another, it cannot be created or destroyed.
Transformations of energy. Although energy can neither be created nor destroyed, it is evident that it may assume many different forms. Thus the falling water may turn the electric generator and produce a current of electricity. The energy lost by the falling water is thus transformed into the energy of the electric current. This in turn may be changed into the energy of motion, as when the current is used for propelling the cars, or into the energy of heat and light, as when it is used for heating and lighting the cars. Again, the energy of coal may be converted into energy of heat and subsequently of motion, as when it is used as a fuel in steam engines.
Since the energy possessed by coal only becomes available when the coal is made to undergo a chemical change, it is sometimes called chemical energy. It is this form of energy in which we are especially interested in the study of chemistry.
Matter. Matter may be defined as that which occupies space and possesses weight. Like energy, matter may be changed oftentimes from one form into another; and since in these transformations all the other physical properties of a substance save weight are likely to change, the inquiry arises, Does the weight also change? Much careful experimenting has shown that it does not. The weight of the products formed in any change in matter always equals the weight of the substances undergoing change.
Law of conservation of matter. The important truth just stated is frequently referred to as the law of conservation of matter, and this law may be briefly stated thus: Matter can neither be created nor destroyed, though it can be changed from one form into another.
Classification of matter. At first sight there appears to be no limit to the varieties of matter of which the world is made. For convenience in study we may classify all these varieties under three heads, namely, mechanical mixtures, chemical compounds, and elements.
Mechanical mixtures. If equal bulks of common salt and iron filings are thoroughly mixed together, a product is obtained which, judging by its appearance, is a new substance. If it is examined more closely, however, it will be seen to be merely a mixture of the salt and iron, each of which substances retains its own peculiar properties. The mixture tastes just like salt; the iron particles can be seen and their gritty character detected. A magnet rubbed in the mixture draws out the iron just as if the salt were not there. On the other hand, the salt can be separated from the iron quite easily. Thus, if several grams of the mixture are placed in a test tube, and the tube half filled with water and thoroughly shaken, the salt dissolves in the water. The iron particles can then be filtered from the liquid by pouring the entire mixture upon a piece of filter paper folded so as to fit into the interior of a funnel (Fig. 1). The paper retains the solid but allows the clear liquid, known as the filtrate, to drain through. The iron particles left upon the filter paper will be found to be identical with the original iron. The salt can be recovered from the filtrate by evaporation of the water. To accomplish this the filtrate is poured into a small evaporating dish and gently heated (Fig. 2) until the water has disappeared, or evaporated. The solid left in the dish is identical in every way with the original salt. Both the iron and the salt have thus been recovered in their original condition. It is evident that no new substance has been formed by rubbing the salt and iron together. The product is called a mechanical mixture. Such mixtures are very common in nature, almost all minerals, sands, and soils being examples of this class of substances. It is at once apparent that there is no law regulating the composition of a mechanical mixture, and no two mixtures are likely to have exactly the same composition. The ingredients of a mechanical mixture can usually be separated by mechanical means, such as sifting, sorting, magnetic attraction, or by dissolving one constituent and leaving the other unchanged.
DEFINITION: A mechanical mixture is one in which the constituents retain their original properties, no chemical action having taken place when they were brought together.
Chemical compounds. If iron filings and powdered sulphur are thoroughly ground together in a mortar, a yellowish-green substance results. It might easily be taken to be a new body; but as in the case of the iron and salt, the ingredients can readily be separated. A magnet draws out the iron. Water does not dissolve the sulphur, but other liquids do, as, for example, the liquid called carbon disulphide. When the mixture is treated with carbon disulphide the iron is left unchanged, and the sulphur can be obtained again, after filtering off the iron, by evaporating the liquid. The substance is, therefore, a mechanical mixture.
If now a new portion of the mixture is placed in a dry test tube and carefully heated in the flame of a Bunsen burner, as shown in Fig. 3, a striking change takes place. The mixture begins to glow at some point, the glow rapidly extending throughout the whole mass. If the test tube is now broken and the product examined, it will be found to be a hard, black, brittle substance, in no way recalling the iron or the sulphur. The magnet no longer attracts it; carbon disulphide will not dissolve sulphur from it. It is a new substance with new properties, resulting from the chemical union of iron and sulphur, and is called iron sulphide. Such substances are called chemical compounds, and differ from mechanical mixtures in that the substances producing them lose their own characteristic properties. We shall see later that the two also differ in that the composition of a chemical compound never varies.
DEFINITION: A chemical compound is a substance the constituents of which have lost their own characteristic properties, and which cannot be separated save by a chemical change.
Elements. It has been seen that iron sulphide is composed of two entirely different substances,—iron and sulphur. The question arises, Do these substances in turn contain other substances, that is, are they also chemical compounds? Chemists have tried in a great many ways to decompose them, but all their efforts have failed. Substances which have resisted all efforts to decompose them into other substances are called elements. It is not always easy to prove that a given substance is really an element. Some way as yet untried may be successful in decomposing it into other simpler forms of matter, and the supposed element will then prove to be a compound. Water, lime, and many other familiar compounds were at one time thought to be elements.
DEFINITION: An element is a substance which cannot be separated into simpler substances by any known means.
Kinds of matter. While matter has been grouped in three classes for the purpose of study, it will be apparent that there are really but two distinct kinds of matter, namely, compounds and elements. A mechanical mixture is not a third distinct kind of matter, but is made up of varying quantities of either compounds or elements or both.
Alchemy. In olden times it was thought that some way could be found to change one element into another, and a great many efforts were made to accomplish this transformation. Most of these efforts were directed toward changing the commoner metals into gold, and many fanciful ways for doing this were described. The chemists of that time were called alchemists, and the art which they practiced was called alchemy. The alchemists gradually became convinced that the only way common metals could be changed into gold was by the wonderful power of a magic substance which they called the philosopher's stone, which would accomplish this transformation by its mere touch and would in addition give perpetual youth to its fortunate possessor. No one has ever found such a stone, and no one has succeeded in changing one metal into another.
Number of elements. The number of substances now considered to be elements is not large—about eighty in all. Many of these are rare, and very few of them make any large fraction of the materials in the earth's crust. Clarke gives the following estimate of the composition of the earth's crust:
Oxygen 47.0% Calcium 3.5% Silicon 27.9 Magnesium 2.5 Aluminium 8.1 Sodium 2.7 Iron 4.7 Potassium 2.4 Other elements 1.2%
A complete list of the elements is given in the Appendix. In this list the more common of the elements are marked with an asterisk. It is not necessary to study more than a third of the total number of elements to gain a very good knowledge of chemistry.
Physical state of the elements. About ten of the elements are gases at ordinary temperatures. Two—mercury and bromine—are liquids. The others are all solids, though their melting points vary through wide limits, from caesium which melts at 26 deg. to elements which do not melt save in the intense heat of the electric furnace.
Occurrence of the elements. Comparatively few of the elements occur as uncombined substances in nature, most of them being found in the form of chemical compounds. When an element does occur by itself, as is the case with gold, we say that it occurs in the free state or native; when it is combined with other substances in the form of compounds, we say that it occurs in the combined state, or in combination. In the latter case there is usually little about the compound to suggest that the element is present in it; for we have seen that elements lose their own peculiar properties when they enter into combination with other elements. It would never be suspected, for example, that the reddish, earthy-looking iron ore contains iron.
Names of elements. The names given to the elements have been selected in a great many different ways. (1) Some names are very old and their original meaning is obscure. Such names are iron, gold, and copper. (2) Many names indicate some striking physical property of the element. The name bromine, for example, is derived from a Greek word meaning a stench, referring to the extremely unpleasant odor of the substance. The name iodine comes from a word meaning violet, alluding to the beautiful color of iodine vapor. (3) Some names indicate prominent chemical properties of the elements. Thus, nitrogen means the producer of niter, nitrogen being a constituent of niter or saltpeter. Hydrogen means water former, signifying its presence in water. Argon means lazy or inert, the element being so named because of its inactivity. (4) Other elements are named from countries or localities, as germanium and scandium.
Symbols. In indicating the elements found in compounds it is inconvenient to use such long names, and hence chemists have adopted a system of abbreviations. These abbreviations are known as symbols, each element having a distinctive symbol. (1) Sometimes the initial letter of the name will suffice to indicate the element. Thus I stands for iodine, C for carbon. (2) Usually it is necessary to add some other characteristic letter to the symbol, since several names may begin with the same letter. Thus C stands for carbon, Cl for chlorine, Cd for cadmium, Ce for cerium, Cb for columbium. (3) Sometimes the symbol is an abbreviation of the old Latin name. In this way Fe (ferrum) indicates iron, Cu (cuprum), copper, Au (aurum), gold. The symbols are included in the list of elements given in the Appendix. They will become familiar through constant use.
Chemical affinity the cause of chemical combination. The agency which causes substances to combine and which holds them together when combined is called chemical affinity. The experiments described in this chapter, however, show that heat is often necessary to bring about chemical action. The distinction between the cause producing chemical action and the circumstances favoring it must be clearly made. Chemical affinity is always the cause of chemical union. Many agencies may make it possible for chemical affinity to act by overcoming circumstances which stand in its way. Among these agencies are heat, light, and electricity. As a rule, solution also promotes action between two substances. Sometimes these agencies may overcome chemical attraction and so occasion the decomposition of a compound.
EXERCISES
1. To what class of changes do the following belong? (a) The melting of ice; (b) the souring of milk; (c) the burning of a candle; (d) the explosion of gunpowder; (e) the corrosion of metals. What test question must be applied in each of the above cases?
2. Give two additional examples (a) of chemical changes; (b) of physical changes.
3. Is a chemical change always accompanied by a physical change? Is a physical change always accompanied by a chemical change?
4. Give two or more characteristics of a chemical change.
5. (a) When a given weight of water freezes, does it absorb or evolve heat? (b) When the resulting ice melts, is the total heat change the same or different from that of freezing?
6. Give three examples of each of the following: (a) mechanical mixtures; (b) chemical compounds; (c) elements.
7. Give the derivation of the names of the following elements: thorium, gallium, selenium, uranium. (Consult dictionary.)
8. Give examples of chemical changes which are produced through the agency of heat; of light; of electricity.
CHAPTER II
OXYGEN
History. The discovery of oxygen is generally attributed to the English chemist Priestley, who in 1774 obtained the element by heating a compound of mercury and oxygen, known as red oxide of mercury. It is probable, however, that the Swedish chemist Scheele had previously obtained it, although an account of his experiments was not published until 1777. The name oxygen signifies acid former. It was given to the element by the French chemist Lavoisier, since he believed that all acids owe their characteristic properties to the presence of oxygen. This view we now know to be incorrect.
Occurrence. Oxygen is by far the most abundant of all the elements. It occurs both in the free and in the combined state. In the free state it occurs in the air, 100 volumes of dry air containing about 21 volumes of oxygen. In the combined state it forms eight ninths of water and nearly one half of the rocks composing the earth's crust. It is also an important constituent of the compounds which compose plant and animal tissues; for example, about 66% by weight of the human body is oxygen.
Preparation. Although oxygen occurs in the free state in the atmosphere, its separation from the nitrogen and other gases with which it is mixed is such a difficult matter that in the laboratory it has been found more convenient to prepare it from its compounds. The most important of the laboratory methods are the following:
1. Preparation from water. Water is a compound, consisting of 11.18% hydrogen and 88.82% oxygen. It is easily separated into these constituents by passing an electric current through it under suitable conditions. The process will be described in the chapter on water. While this method of preparation is a simple one, it is not economical.
2. Preparation from mercuric oxide. This method is of interest, since it is the one which led to the discovery of oxygen. The oxide, which consists of 7.4% oxygen and 92.6% mercury, is placed in a small, glass test tube and heated. The compound is in this way decomposed into mercury which collects on the sides of the glass tube, forming a silvery mirror, and oxygen which, being a gas, escapes from the tube. The presence of the oxygen is shown by lighting the end of a splint, extinguishing the flame and bringing the glowing coal into the mouth of the tube. The oxygen causes the glowing coal to burst into a flame.
In a similar way oxygen may be obtained from its compounds with some of the other elements. Thus manganese dioxide, a black compound of manganese and oxygen, when heated to about 700 deg., loses one third of its oxygen, while barium dioxide, when heated, loses one half of its oxygen.
3. Preparation from potassium chlorate (usual laboratory method). Potassium chlorate is a white solid which consists of 31.9% potassium, 28.9% chlorine, and 39.2% oxygen. When heated it undergoes a series of changes in which all the oxygen is finally set free, leaving a compound of potassium and chlorine called potassium chloride. The change may be represented as follows:
/potassium (potassium / potassium (potassium { chlorine } = { } + oxygen chlorate) chlorine / chloride) oxygen /
The evolution of the oxygen begins at about 400 deg.. It has been found, however, that if the potassium chlorate is mixed with about one fourth its weight of manganese dioxide, the oxygen is given off at a much lower temperature. Just how the manganese dioxide brings about this result is not definitely known. The amount of oxygen obtained from a given weight of potassium chlorate is exactly the same whether the manganese dioxide is present or not. So far as can be detected the manganese dioxide undergoes no change.
Directions for preparing oxygen. The manner of preparing oxygen from potassium chlorate is illustrated in the accompanying diagram (Fig. 4). A mixture consisting of one part of manganese dioxide and four parts of potassium chlorate is placed in the flask A and gently heated. The oxygen is evolved and escapes through the tube B. It is collected by bringing over the end of the tube the mouth of a bottle completely filled with water and inverted in a vessel of water, as shown in the figure. The gas rises in the bottle and displaces the water. In the preparation of large quantities of oxygen, a copper retort (Fig. 5) is often substituted for the glass flask.
In the preparation of oxygen from potassium chlorate and manganese dioxide, the materials used must be pure, otherwise a violent explosion may occur. The purity of the materials is tested by heating a small amount of the mixture in a test tube.
The collection of gases. The method used for collecting oxygen illustrates the general method used for collecting such gases as are insoluble in water or nearly so. The vessel C (Fig. 4), containing the water in which the bottles are inverted, is called a pneumatic trough.
Commercial methods of preparation. Oxygen can now be purchased stored under great pressure in strong steel cylinders (Fig. 6). It is prepared either by heating a mixture of potassium chlorate and manganese dioxide, or by separating it from the nitrogen and other gases with which it is mixed in the atmosphere. The methods employed for effecting this separation will be described in subsequent chapters.
Physical properties. Oxygen is a colorless, odorless, tasteless gas, slightly heavier than air. One liter of it, measured at a temperature of 0 deg. and under a pressure of one atmosphere, weighs 1.4285 g., while under similar conditions one liter of air weighs 1.2923 g. It is but slightly soluble in water. Oxygen, like other gases, may be liquefied by applying very great pressure to the highly cooled gas. When the pressure is removed the liquid oxygen passes again into the gaseous state, since its boiling point under ordinary atmospheric pressure is -182.5 deg..
Chemical properties. At ordinary temperatures oxygen is not very active chemically. Most substances are either not at all affected by it, or the action is so slow as to escape notice. At higher temperatures, however, it is very active, and unites directly with most of the elements. This activity may be shown by heating various substances until just ignited and then bringing them into vessels of the gas, when they will burn with great brilliancy. Thus a glowing splint introduced into a jar of oxygen bursts into flame. Sulphur burns in the air with a very weak flame and feeble light; in oxygen, however, the flame is increased in size and brightness. Substances which readily burn in air, such as phosphorus, burn in oxygen with dazzling brilliancy. Even substances which burn in air with great difficulty, such as iron, readily burn in oxygen.
The burning of a substance in oxygen is due to the rapid combination of the substance or of the elements composing it with the oxygen. Thus, when sulphur burns both the oxygen and sulphur disappear as such and there is formed a compound of the two, which is an invisible gas, having the characteristic odor of burning sulphur. Similarly, phosphorus on burning forms a white solid compound of phosphorus and oxygen, while iron forms a reddish-black compound of iron and oxygen.
Oxidation. The term oxidation is applied to the chemical change which takes place when a substance, or one of its constituent parts, combines with oxygen. This process may take place rapidly, as in the burning of phosphorus, or slowly, as in the oxidation (or rusting) of iron when exposed to the air. It is always accompanied by the liberation of heat. The amount of heat liberated by the oxidation of a definite weight of any given substance is always the same, being entirely independent of the rapidity of the process. If the oxidation takes place slowly, the heat is generated so slowly that it is difficult to detect it. If the oxidation takes place rapidly, however, the heat is generated in such a short interval of time that the substance may become white hot or burst into a flame.
Combustion; kindling temperature. When oxidation takes place so rapidly that the heat generated is sufficient to cause the substance to glow or burst into a flame the process is called combustion. In order that any substance may undergo combustion, it is necessary that it should be heated to a certain temperature, known as the kindling temperature. This temperature varies widely for different bodies, but is always definite for the same body. Thus the kindling temperature of phosphorus is far lower than that of iron, but is definite for each. When any portion of a substance is heated until it begins to burn the combustion will continue without the further application of heat, provided the heat generated by the process is sufficient to bring other parts of the substance to the kindling temperature. On the other hand, if the heat generated is not sufficient to maintain the kindling temperature, combustion ceases.
Oxides. The compounds formed by the oxidation of any element are called oxides. Thus in the combustion of sulphur, phosphorus, and iron, the compounds formed are called respectively oxide of sulphur, oxide of phosphorus, and oxide of iron. In general, then, an oxide is a compound of oxygen with another element. A great many substances of this class are known; in fact, the oxides of all the common elements have been prepared, with the exception of those of fluorine and bromine. Some of these are familiar compounds. Water, for example, is an oxide of hydrogen, and lime an oxide of the metal calcium.
Products of combustion. The particular oxides formed by the combustion of any substance are called products of combustion of that substance. Thus oxide of sulphur is the product of the combustion of sulphur; oxide of iron is the product of the combustion of iron. It is evident that the products of the combustion of any substance must weigh more than the original substance, the increase in weight corresponding to the amount of oxygen taken up in the act of combustion. For example, when iron burns the oxide of iron formed weighs more than the original iron.
In some cases the products of combustion are invisible gases, so that the substance undergoing combustion is apparently destroyed. Thus, when a candle burns it is consumed, and so far as the eye can judge nothing is formed during combustion. That invisible gases are formed, however, and that the weight of these is greater than the weight of the candle may be shown by the following experiment.
A lamp chimney is filled with sticks of the compound known as sodium hydroxide (caustic soda), and suspended from the beam of the balance, as shown in Fig. 7. A piece of candle is placed on the balance pan so that the wick comes just below the chimney, and the balance is brought to a level by adding weights to the other pan. The candle is then lighted. The products formed pass up through the chimney and are absorbed by the sodium hydroxide. Although the candle burns away, the pan upon which it rests slowly sinks, showing that the combustion is attended by an increase in weight.
Combustion in air and in oxygen. Combustion in air and in oxygen differs only in rapidity, the products formed being exactly the same. That the process should take place less rapidly in the former is readily understood, for the air is only about one fifth oxygen, the remaining four fifths being inert gases. Not only is less oxygen available, but much of the heat is absorbed in raising the temperature of the inert gases surrounding the substance undergoing combustion, and the temperature reached in the combustion is therefore less.
Phlogiston theory of combustion. The French chemist Lavoisier (1743-1794), who gave to oxygen its name was the first to show that combustion is due to union with oxygen. Previous to his time combustion was supposed to be due to the presence of a substance or principle called phlogiston. One substance was thought to be more combustible than another because it contained more phlogiston. Coal, for example, was thought to be very rich in phlogiston. The ashes left after combustion would not burn because all the phlogiston had escaped. If the phlogiston could be restored in any way, the substance would then become combustible again. Although this view seems absurd to us in the light of our present knowledge, it formerly had general acceptance. The discovery of oxygen led Lavoisier to investigate the subject, and through his experiments he arrived at the true explanation of combustion. The discovery of oxygen together with the part it plays in combustion is generally regarded as the most important discovery in the history of chemistry. It marked the dawn of a new period in the growth of the science.
Combustion in the broad sense. According to the definition given above, the presence of oxygen is necessary for combustion. The term is sometimes used, however, in a broader sense to designate any chemical change attended by the evolution of heat and light. Thus iron and sulphur, or hydrogen and chlorine under certain conditions, will combine so rapidly that light is evolved, and the action is called a combustion. Whenever combustion takes place in the air, however, the process is one of oxidation.
Spontaneous combustion. The temperature reached in a given chemical action, such as oxidation, depends upon the rate at which the reaction takes place. This rate is usually increased by raising the temperature of the substances taking part in the action.
When a slow oxidation takes place under such conditions that the heat generated is not lost by being conducted away, the temperature of the substance undergoing oxidation is raised, and this in turn hastens the rate of oxidation. The rise in temperature may continue in this way until the kindling temperature of the substance is reached, when combustion begins. Combustion occurring in this way is called spontaneous combustion.
Certain oils, such as the linseed oil used in paints, slowly undergo oxidation at ordinary temperatures, and not infrequently the origin of fires has been traced to the spontaneous combustion of oily rags. The spontaneous combustion of hay has been known to set barns on fire. Heaps of coal have been found to be on fire when spontaneous combustion offered the only possible explanation.
Importance of oxygen. 1. Oxygen is essential to life. Among living organisms only certain minute forms of plant life can exist without it. In the process of respiration the air is taken into the lungs where a certain amount of oxygen is absorbed by the blood. It is then carried to all parts of the body, oxidizing the worn-out tissues and changing them into substances which may readily be eliminated from the body. The heat generated by this oxidation is the source of the heat of the body. The small amount of oxygen which water dissolves from the air supports all the varied forms of aquatic animals.
2. Oxygen is also essential to decay. The process of decay is really a kind of oxidation, but it will only take place in the presence of certain minute forms of life known as bacteria. Just how these assist in the oxidation is not known. By this process the dead products of animal and vegetable life which collect on the surface of the earth are slowly oxidized and so converted into harmless substances. In this way oxygen acts as a great purifying agent.
3. Oxygen is also used in the treatment of certain diseases in which the patient is unable to inhale sufficient air to supply the necessary amount of oxygen.
OZONE
Preparation. When electric sparks are passed through oxygen or air a small percentage of the oxygen is converted into a substance called ozone, which differs greatly from oxygen in its properties. The same change can also be brought about by certain chemical processes. Thus, if some pieces of phosphorus are placed in a bottle and partially covered with water, the presence of ozone may soon be detected in the air contained in the bottle. The conversion of oxygen into ozone is attended by a change in volume, 3 volumes of oxygen forming 2 volumes of ozone. If the resulting ozone is heated to about 300 deg., the reverse change takes place, the 2 volumes of ozone being changed back into 3 volumes of oxygen. It is possible that traces of ozone exist in the atmosphere, although its presence there has not been definitely proved, the tests formerly used for its detection having been shown to be unreliable.
Properties. As commonly prepared, ozone is mixed with a large excess of oxygen. It is possible, however, to separate the ozone and thus obtain it in pure form. The gas so obtained has the characteristic odor noticed about electrical machines when in operation. By subjecting it to great pressure and a low temperature, the gas condenses to a bluish liquid, boiling at -119 deg.. When unmixed with other gases ozone is very explosive, changing back into oxygen with the liberation of heat. Its chemical properties are similar to those of oxygen except that it is far more active. Air or oxygen containing a small amount of ozone is now used in place of oxygen in certain manufacturing processes.
The difference between oxygen and ozone. Experiments show that in changing oxygen into ozone no other kind of matter is either added to the oxygen or withdrawn from it. The question arises then, How can we account for the difference in their properties? It must be remembered that in all changes we have to take into account energy as well as matter. By changing the amount of energy in a substance we change its properties. That oxygen and ozone contain different amounts of energy may be shown in a number of ways; for example, by the fact that the conversion of ozone into oxygen is attended by the liberation of heat. The passage of the electric sparks through oxygen has in some way changed the energy content of the element and thus it has acquired new properties. Oxygen and ozone must, therefore, be regarded as identical so far as the kind of matter of which they are composed is concerned. Their different properties are due to their different energy contents.
Allotropic states or forms of matter. Other elements besides oxygen may exist in more than one form. These different forms of the same element are called allotropic states or forms of the element. These forms differ not only in physical properties but also in their energy contents. Elements often exist in a variety of forms which look quite different. These differences may be due to accidental causes, such as the size or shape of the particles or the way in which the element was prepared. Only such forms, however, as have different energy contents are properly called allotropic forms.
MEASUREMENT OF GAS VOLUMES
Standard conditions. It is a well-known fact that the volume occupied by a definite weight of any gas can be altered by changing the temperature of the gas or the pressure to which it is subjected. In measuring the volume of gases it is therefore necessary, for the sake of accuracy, to adopt some standard conditions of temperature and pressure. The conditions agreed upon are (1) a temperature of 0 deg., and (2) a pressure equal to the average pressure exerted by the atmosphere at the sea level, that is, 1033.3 g. per square centimeter. These conditions of temperature and pressure are known as the standard conditions, and when the volume of a gas is given it is understood that the measurement was made under these conditions, unless it is expressly stated otherwise. For example, the weight of a liter of oxygen has been given as 1.4285 g. This means that one liter of oxygen, measured at a temperature of 0 deg. and under a pressure of 1033.3 g. per square centimeter, weighs 1.4285 g.
The conditions which prevail in the laboratory are never the standard conditions. It becomes necessary, therefore, to find a way to calculate the volume which a gas will occupy under standard conditions from the volume which it occupies under any other conditions. This may be done in accordance with the following laws.
Law of Charles. This law expresses the effect which a change in the temperature of a gas has upon its volume. It may be stated as follows: For every degree the temperature of a gas rises above zero the volume of the gas is increased by 1/273 of the volume which it occupies at zero; likewise for every degree the temperature of the gas falls below zero the volume of the gas is decreased by 1/273 of the volume which it occupies at zero, provided in both cases that the pressure to which the gas is subjected remains constant.
If V represents the volume of gas at 0 deg., then the volume at 1 deg. will be V + 1/273 V; at 2 deg. it will be V + 2/273 V; or, in general, the volume v, at the temperature t, will be expressed by the formula
(1) v = V + t/273 V,
or (2) v = V(1 + (t/273)).
Since 1/273 = 0.00366, the formula may be written
(3) v = V(1 + 0.00366t).
Since the value of V (volume under standard conditions) is the one usually sought, it is convenient to transpose the equation to the following form:
(4) V = v/(1 + 0.00366t).
The following problem will serve as an illustration of the application of this equation.
The volume of a gas at 20 deg. is 750 cc.; find the volume it will occupy at 0 deg., the pressure remaining constant.
In this case, v = 750 cc. and t = 20. By substituting these values, equation (4) becomes
V = 750/(1 + 0.00366 x 20) = 698.9 cc.
Law of Boyle. This law expresses the relation between the volume occupied by a gas and the pressure to which it is subjected. It may be stated as follows: The volume of a gas is inversely proportional to the pressure under which it is measured, provided the temperature of the gas remains constant.
If V represents the volume when subjected to a pressure P and v represents its volume when the pressure is changed to p, then, in accordance with the above law, V : v :: p : P, or VP = vp. In other words, for a given weight of a gas the product of the numbers representing its volume and the pressure to which it is subjected is a constant.
Since the pressure of the atmosphere at any point is indicated by the barometric reading, it is convenient in the solution of the problems to substitute the latter for the pressure measured in grams per square centimeter. The average reading of the barometer at the sea level is 760 mm., which corresponds to a pressure of 1033.3 g. per square centimeter. The following problem will serve as an illustration of the application of Boyle's law.
A gas occupies a volume of 500 cc. in a laboratory where the barometric reading is 740 mm. What volume would it occupy if the atmospheric pressure changed so that the reading became 750 mm.?
Substituting the values in the equation VP = vp, we have 500 x 740 = v x 750, or v = 493.3 cc.
Variations in the volume of a gas due to changes both in temperature and pressure. Inasmuch as corrections must be made as a rule for both temperature and pressure, it is convenient to combine the equations given above for the corrections for each, so that the two corrections may be made in one operation. The following equation is thus obtained:
(5) V_{s} = vp/(760(1 + 0.00366t)),
in which V_{s} represents the volume of a gas under standard conditions and v, p, and t the volume, pressure, and temperature respectively at which the gas was actually measured.
The following problem will serve to illustrate the application of this equation.
A gas having a temperature of 20 deg. occupies a volume of 500 cc. when subjected to a pressure indicated by a barometric reading of 740 mm. What volume would this gas occupy under standard conditions?
In this problem v = 500, p = 740, and t = 20. Substituting these values in the above equation, we get
V_{s} = (500 x 740)/(760 (1 + 0.00366 x 20)) = 453.6 cc.
Variations in the volume of a gas due to the pressure of aqueous vapor. In many cases gases are collected over water, as explained under the preparation of oxygen. In such cases there is present in the gas a certain amount of water vapor. This vapor exerts a definite pressure, which acts in opposition to the atmospheric pressure and which therefore must be subtracted from the latter in determining the effective pressure upon the gas. Thus, suppose we wish to determine the pressure to which the gas in tube A (Fig. 8) is subjected. The tube is raised or lowered until the level of the water inside and outside the tube is the same. The atmosphere presses down upon the surface of the water (as indicated by the arrows), thus forcing the water upward within the tube with a pressure equal to the atmospheric pressure. The full force of this upward pressure, however, is not spent in compressing the gas within the tube, for since it is collected over water it contains a certain amount of water vapor. This water vapor exerts a pressure (as indicated by the arrow within the tube) in opposition to the upward pressure. It is plain, therefore, that the effective pressure upon the gas is equal to the atmospheric pressure less the pressure exerted by the aqueous vapor. The pressure exerted by the aqueous vapor increases with the temperature. The figures representing the extent of this pressure (often called the tension of aqueous vapor) are given in the Appendix. They express the pressure or tension in millimeters of mercury, just as the atmospheric pressure is expressed in millimeters of mercury. Representing the pressure of the aqueous vapor by a, formula (5) becomes
(6) V_{s} = v(p - a)/(760(1 + 0.00366t)).
The following problem will serve to illustrate the method of applying the correction for the pressure of the aqueous vapor.
The volume of a gas measured over water in a laboratory where the temperature is 20 deg. and the barometric reading is 740 mm. is 500 cc. What volume would this occupy under standard conditions?
The pressure exerted by the aqueous vapor at 20 deg. (see table in Appendix) is equal to the pressure exerted by a column of mercury 17.4 mm. in height. Substituting the values of v, t, p, and a in formula (6), we have
(6) V_{s} = 500(740 - 17.4)/(760(1 + 0.00366 x 20)) = 442.9 cc.
Adjustment of tubes before reading gas volumes. In measuring the volumes of gases collected in graduated tubes or other receivers, over a liquid as illustrated in Fig. 8, the reading should be taken after raising or lowering the tube containing the gas until the level of the liquid inside and outside the tube is the same; for it is only under these conditions that the upward pressure within the tube is the same as the atmospheric pressure.
EXERCISES
1. What is the meaning of the following words? phlogiston, ozone, phosphorus. (Consult dictionary.)
2. Can combustion take place without the emission of light?
3. Is the evolution of light always produced by combustion?
4. (a) What weight of oxygen can be obtained from 100 g. of water? (b) What volume would this occupy under standard conditions?
5. (a) What weight of oxygen can be obtained from 500g. of mercuric oxide? (b) What volume would this occupy under standard conditions?
6. What weight of each of the following compounds is necessary to prepare 50 l. of oxygen? (a) water; (b) mercuric oxide; (c) potassium chlorate.
7. Reduce the following volumes to 0 deg., the pressure remaining constant: (a) 150 cc. at 10 deg.; (b) 840 cc. at 273 deg..
8. A certain volume of gas is measured when the temperature is 20 deg.. At what temperature will its volume be doubled?
9. Reduce the following volumes to standard conditions of pressure, the temperature remaining constant: (a) 200 cc. at 740 mm.; (b) 500 l. at 380 mm.
10. What is the weight of 1 l. of oxygen when the pressure is 750 mm. and the temperature 0 deg.?
11. Reduce the following volumes to standard conditions of temperature and pressure: (a) 340 cc. at 12 deg. and 753 mm; (b) 500 cc. at 15 deg. and 740 mm.
12. What weight of potassium chlorate is necessary to prepare 250 l. of oxygen at 20 deg. and 750 mm.?
13. Assuming the cost of potassium chlorate and mercuric oxide to be respectively $0.50 and $1.50 per kilogram, calculate the cost of materials necessary for the preparation of 50 l. of oxygen from each of the above compounds.
14. 100 g. of potassium chlorate and 25 g. of manganese dioxide were heated in the preparation of oxygen. What products were left in the flask, and how much of each was present?
CHAPTER III
HYDROGEN
Historical. The element hydrogen was first clearly recognized as a distinct substance by the English investigator Cavendish, who in 1766 obtained it in a pure state, and showed it to be different from the other inflammable airs or gases which had long been known. Lavoisier gave it the name hydrogen, signifying water former, since it had been found to be a constituent of water.
Occurrence. In the free state hydrogen is found in the atmosphere, but only in traces. In the combined state it is widely distributed, being a constituent of water as well as of all living organisms, and the products derived from them, such as starch and sugar. About 10% of the human body is hydrogen. Combined with carbon, it forms the substances which constitute petroleum and natural gas.
It is an interesting fact that while hydrogen in the free state occurs only in traces on the earth, it occurs in enormous quantities in the gaseous matter surrounding the sun and certain other stars.
Preparation from water. Hydrogen can be prepared from water by several methods, the most important of which are the following.
1. By the electric current. As has been indicated in the preparation of oxygen, water is easily separated into its constituents, hydrogen and oxygen, by passing an electric current through it under certain conditions.
2. By the action of certain metals. When brought into contact with certain metals under appropriate conditions, water gives up a portion or the whole of its hydrogen, its place being taken by the metal. In the case of a few of the metals this change occurs at ordinary temperatures. Thus, if a bit of sodium is thrown on water, an action is seen to take place at once, sufficient heat being generated to melt the sodium, which runs about on the surface of the water. The change which takes place consists in the displacement of one half of the hydrogen of the water by the sodium, and may be represented as follows:
hydrogen sodium sodium + hydrogen (water) = hydrogen (sodium hydroxide) + hydrogen oxygen oxygen
The sodium hydroxide formed is a white solid which remains dissolved in the undecomposed water, and may be obtained by evaporating the solution to dryness. The hydrogen is evolved as a gas and may be collected by suitable apparatus.
Other metals, such as magnesium and iron, decompose water rapidly, but only at higher temperatures. When steam is passed over hot iron, for example, the iron combines with the oxygen of the steam, thus displacing the hydrogen. Experiments show that the change may be represented as follows:
hydrogen iron + hydrogen (water) = iron (iron oxide) + hydrogen oxygen oxygen hydrogen
The iron oxide formed is a reddish-black compound, identical with that obtained by the combustion of iron in oxygen.
Directions for preparing hydrogen by the action of steam on iron. The apparatus used in the preparation of hydrogen from iron and steam is shown in Fig. 9. A porcelain or iron tube B, about 50 cm. in length and 2 cm. or 3 cm. in diameter, is partially filled with fine iron wire or tacks and connected as shown in the figure. The tube B is heated, slowly at first, until the iron is red-hot. Steam is then conducted through the tube by boiling the water in the flask A. The hot iron combines with the oxygen in the steam, setting free the hydrogen, which is collected over water. The gas which first passes over is mixed with the air previously contained in the flask and tube, and is allowed to escape, since a mixture of hydrogen with oxygen or air explodes violently when brought in contact with a flame. It is evident that the flask A must be disconnected from the tube before the heat is withdrawn.
That the gas obtained is different from air and oxygen may be shown by holding a bottle of it mouth downward and bringing a lighted splint into it. The hydrogen is ignited and burns with an almost colorless flame.
Preparation from acids (usual laboratory method). While hydrogen can be prepared from water, either by the action of the electric current or by the action of certain metals, these methods are not economical and are therefore but little used. In the laboratory hydrogen is generally prepared from compounds known as acids, all of which contain hydrogen. When acids are brought in contact with certain metals, the metals dissolve and set free the hydrogen of the acid. Although this reaction is a quite general one, it has been found most convenient in preparing hydrogen by this method to use either zinc or iron as the metal and either hydrochloric or sulphuric acid as the acid. Hydrochloric acid is a compound consisting of 2.77% hydrogen and 97.23% chlorine, while sulphuric acid consists of 2.05% hydrogen, 32.70% sulphur, and 65.25% oxygen.
The changes which take place in the preparation of hydrogen from zinc and sulphuric acid (diluted with water) may be represented as follows:
hydrogen (sulphuric zinc (zinc zinc + sulphur acid) = sulphur sulphate) + hydrogen oxygen oxygen
In other words, the zinc has taken the place of the hydrogen in sulphuric acid. The resulting compound contains zinc, sulphur, and oxygen, and is known as zinc sulphate. This remains dissolved in the water present in the acid. It may be obtained in the form of a white solid by evaporating the liquid left after the metal has passed into solution.
When zinc and hydrochloric acid are used the following changes take place:
hydrogen (hydrochloric zinc (zinc zinc + chlorine acid) = chlorine chloride) + hydrogen
When iron is used the changes which take place are exactly similar to those just given for zinc.
Directions for preparing hydrogen from acids. The preparation of hydrogen from acids is carried out in the laboratory as follows: The metal is placed in a flask or wide-mouthed bottle A (Fig. 10) and the acid is added slowly through the funnel tube B. The metal dissolves in the acid, while the hydrogen which is liberated escapes through the exit tube C and is collected over water. It is evident that the hydrogen which passes over first is mixed with the air from the bottle A. Hence care must be taken not to bring a flame near the exit tube, since, as has been stated previously, such a mixture explodes with great violence when brought in contact with a flame.
Precautions. Both sulphuric acid and zinc, if impure, are likely to contain small amounts of arsenic. Such materials should not be used in preparing hydrogen, since the arsenic present combines with a portion of the hydrogen to form a very poisonous gas known as arsine. On the other hand, chemically pure sulphuric acid, i.e. sulphuric acid that is entirely free from impurities, will not act upon chemically pure zinc. The reaction may be started, however, by the addition of a few drops of a solution of copper sulphate or platinum tetrachloride.
Physical properties. Hydrogen is similar to oxygen in that it is a colorless, tasteless, odorless gas. It is characterized by its extreme lightness, being the lightest of all known substances. One liter of the gas weighs only 0.08984 g. On comparing this weight with that of an equal volume of oxygen, viz., 1.4285 g., the latter is found to be 15.88 times as heavy as hydrogen. Similarly, air is found to be 14.38 times as heavy as hydrogen. Soap bubbles blown with hydrogen rapidly rise in the air. On account of its lightness it is possible to pour it upward from one bottle into another. Thus, if the bottle A (Fig. 11) is filled with hydrogen, placed mouth downward by the side of bottle B, filled with air, and is then gradually inverted under B as indicated in the figure, the hydrogen will flow upward into bottle B, displacing the air. Its presence in bottle B may then be shown by bringing a lighted splint to the mouth of the bottle, when the hydrogen will be ignited by the flame. It is evident, from this experiment, that in order to retain the gas in an open bottle the bottle must be placed mouth downward.
Hydrogen is far more difficult to liquefy than any other gas, with the exception of helium, a rare element recently found to exist in the atmosphere. The English scientist Dewar, however, in 1898 succeeded not only in obtaining hydrogen in liquid state but also as a solid. Liquid hydrogen is colorless and has a density of only 0.07. Its boiling point under atmospheric pressure is -252 deg.. Under diminished pressure the temperature has been reduced to -262 deg.. The solubility of hydrogen in water is very slight, being still less than that of oxygen.
Pure hydrogen produces no injurious results when inhaled. Of course one could not live in an atmosphere of the gas, since oxygen is essential to respiration.
Chemical properties. At ordinary temperatures hydrogen is not an active element. A mixture of hydrogen and chlorine, however, will combine with explosive violence at ordinary temperature if exposed to the sunlight. The union can be brought about also by heating. The product formed in either case is hydrochloric acid. Under suitable conditions hydrogen combines with nitrogen to form ammonia, and with sulphur to form the foul-smelling gas, hydrogen sulphide. The affinity of hydrogen for oxygen is so great that a mixture of hydrogen and oxygen or hydrogen and air explodes with great violence when heated to the kindling temperature (about 612 deg.). Nevertheless under proper conditions hydrogen may be made to burn quietly in either oxygen or air. The resulting hydrogen flame is almost colorless and is very hot. The combustion of the hydrogen is, of course, due to its union with oxygen. The product of the combustion is therefore a compound of hydrogen and oxygen. That this compound is water may be shown easily by experiment.
Directions for burning hydrogen in air. The combustion of hydrogen in air may be carried out safely as follows: The hydrogen is generated in the bottle A (Fig. 12), is dried by conducting it through the tube X, filled with some substance (generally calcium chloride) which has a great attraction for moisture, and escapes through the tube T, the end of which is drawn out to a jet. The hydrogen first liberated mixes with the air contained in the generator. If a flame is brought near the jet before this mixture has all escaped, a violent and very dangerous explosion results, since the entire apparatus is filled with the explosive mixture. On the other hand, if the flame is not applied until all the air has been expelled, the hydrogen is ignited and burns quietly, since only the small amount of it which escapes from the jet can come in contact with the oxygen of the air at any one time. By holding a cold, dry bell jar or bottle over the flame, in the manner shown in the figure, the steam formed by the combustion of the hydrogen is condensed, the water collecting in drops on the sides of the jar.
Precautions. In order to avoid danger it is absolutely necessary to prove that the hydrogen is free from air before igniting it. This can be done by testing small amounts of the escaping gas. A convenient and safe method of doing this is to fill a test tube with the gas by inverting it over the jet. The hydrogen, on account of its lightness, collects in the tube, displacing the air. After holding it over the jet for a few moments in order that it may be filled with the gas, the tube is gently brought, mouth downward, to the flame of a burner placed not nearer than an arm's length from the jet. If the hydrogen is mixed with air a slight explosion occurs, but if pure it burns quietly in the tube. The operation is repeated until the gas burns quietly, when the tube is quickly brought back over the jet for an instant, whereby the escaping hydrogen is ignited by the flame in the tube.
A mixture of hydrogen and oxygen is explosive. That a mixture of hydrogen and air is explosive may be shown safely as follows: A cork through which passes a short glass tube about 1 cm. in diameter is fitted air-tight into the tubule of a bell jar of 2 l. or 3 l. capacity. (A thick glass bottle with bottom removed may be used.) The tube is closed with a small rubber stopper and the bell jar filled with hydrogen, the gas being collected over water. When entirely filled with the gas the jar is removed from the water and supported by blocks of wood in order to leave the bottom of the jar open, as shown in Fig. 13. The stopper is now removed from the tube in the cork, and the hydrogen, which on account of its lightness escapes from the tube, is at once lighted. As the hydrogen escapes, the air flows in at the bottom of the jar and mixes with the remaining portion of the hydrogen, so that a mixture of the two soon forms, and a loud explosion results. The explosion is not dangerous, since the bottom of the jar is open, thus leaving room for the expansion of the hot gas.
Since air is only one fifth oxygen, the remainder being inert gases, it may readily be inferred that a mixture of hydrogen with pure oxygen would be far more explosive than a mixture of hydrogen with air. Such mixtures should not be made except in small quantities and by experienced workers.
Hydrogen does not support combustion. While hydrogen is readily combustible, it is not a supporter of combustion. In other words, substances will not burn in it. This may be shown by bringing a lighted candle supported by a stiff wire into a bottle or cylinder of the pure gas, as shown in Fig. 14. The hydrogen is ignited by the flame of the candle and burns at the mouth of the bottle, where it comes in contact with the oxygen in the air. When the candle is thrust up into the gas, its flame is extinguished on account of the absence of oxygen. If slowly withdrawn, the candle is relighted as it passes through the layer of burning hydrogen.
Reduction. On account of its great affinity for oxygen, hydrogen has the power of abstracting it from many of its compounds. Thus, if a stream of hydrogen, dried by passing through the tube B (Fig. 15), filled with calcium chloride, is conducted through the tube C containing some copper oxide, heated to a moderate temperature, the hydrogen abstracts the oxygen from the copper oxide. The change may be represented as follows:
hydrogen + {copper} {hydrogen} {oxygen}(copper oxide) = {oxygen }(water) + copper
The water formed collects in the cold portions of the tube C near its end. In this experiment the copper oxide is said to undergo reduction. Reduction may therefore be defined as the process of withdrawing oxygen from a compound.
Relation of reduction to oxidation. At the same time that the copper oxide is reduced it is clear that the hydrogen is oxidized, for it combines with the oxygen given up by the copper oxide. The two processes are therefore very closely related, and it usually happens that when one substance is oxidized some other substance is reduced. That substance which gives up its oxygen is called an oxidizing agent, while the substance which unites with the oxygen is called a reducing agent.
The oxyhydrogen blowpipe. This is a form of apparatus used for burning hydrogen in pure oxygen. As has been previously stated, the flame produced by the combustion of hydrogen in the air is very hot. It is evident that if pure oxygen is substituted for air, the temperature reached will be much higher, since there are no inert gases to absorb the heat. The oxyhydrogen blowpipe, used to effect this combination, consists of a small tube placed within a larger one, as shown in Fig. 16.
The hydrogen, stored under pressure, generally in steel cylinders, is first passed through the outer tube and ignited at the open end of the tube. The oxygen from a similar cylinder is then conducted through the inner tube, and mixes with the hydrogen at the end of the tube. In order to produce the maximum heat, the hydrogen and oxygen must be admitted to the blowpipe in the exact proportion in which they combine, viz., 2 volumes of hydrogen to 1 of oxygen, or by weight, 1 part of hydrogen to 7.94 parts of oxygen. The intensity of the heat may be shown by bringing into the flame pieces of metal such as iron wire or zinc. These burn with great brilliancy. Even platinum, having a melting point of 1779 deg., may be melted by the heat of the flame.
While the oxyhydrogen flame is intensely hot, it is almost non-luminous. If directed against some infusible substance like ordinary lime (calcium oxide), the heat is so intense that the lime becomes incandescent and glows with a brilliant light. This is sometimes used as a source of light, under the name of Drummond or lime light.
The blast lamp. A similar form of apparatus is commonly used in the laboratory as a source of heat under the name blast lamp (Fig. 17). This differs from the oxyhydrogen blowpipe only in the size of the tubes. In place of the hydrogen and oxygen the more accessible coal gas and air are respectively used. The former is composed largely of a mixture of free hydrogen and gaseous compounds of carbon and hydrogen. While the temperature of the flame is not so high as that of the oxyhydrogen blowpipe, it nevertheless suffices for most chemical operations carried out in the laboratory.
Uses of hydrogen. On account of its cost, hydrogen is but little used for commercial purposes. It is sometimes used as a material for the inflation of balloons, but usually the much cheaper coal gas is substituted for it. Even hot air is often used when the duration of ascension is very short. It has been used also as a source of heat and light in the oxyhydrogen blowpipe. Where the electric current is available, however, this form of apparatus has been displaced almost entirely by the electric light and electric furnace, which are much more economical and more powerful sources of light and heat.
EXERCISES
1. Will a definite weight of iron decompose an unlimited weight of steam?
2. Why is oxygen passed through the inner tube of the oxyhydrogen blowpipe rather than the outer?
3. In Fig. 14, will the flame remain at the mouth of the tube?
4. From Fig. 15, suggest a way for determining experimentally the quantity of water formed in the reaction.
5. Distinguish clearly between the following terms: oxidation, reduction, combustion, and kindling temperature.
6. Is oxidation always accompanied by reduction?
7. What is the source of heat in the lime light? What is the exact use of lime in this instrument?
8. In Fig. 12, why is it necessary to dry the hydrogen by means of the calcium chloride in the tube X?
9. At what pressure would the weight of 1 l. of hydrogen be equal to that of oxygen under standard conditions?
10. (a) What weight of hydrogen can be obtained from 150 g. of sulphuric acid? (b) What volume would this occupy under standard conditions? (c) The density of sulphuric acid is 1.84. What volume would the 150 g. of the acid occupy?
11. How many liters of hydrogen can be obtained from 50 cc. of sulphuric acid having a density of 1.84?
12. Suppose you wish to fill five liter bottles with hydrogen, the gas to be collected over water in your laboratory, how many cubic centimeters of sulphuric acid would be required?
CHAPTER IV
COMPOUNDS OF HYDROGEN AND OXYGEN; WATER AND HYDROGEN DIOXIDE
WATER
Historical. Water was long regarded as an element. In 1781 Cavendish showed that it is formed by the union of hydrogen and oxygen. Being a believer in the phlogiston theory, however, he failed to interpret his results correctly. A few years later Lavoisier repeated Cavendish's experiments and showed that water must be regarded as a compound of hydrogen and oxygen.
General methods employed for the determination of the composition of a compound. The composition of a compound may be determined by either of two general processes these are known as analysis and synthesis.
1. Analysis is the process of decomposing a compound into its constituents and determining what these constituents are. The analysis is qualitative when it results in merely determining what elements compose the compound; it is quantitative when the exact percentage of each constituent is determined. Qualitative analysis must therefore precede quantitative analysis, for it must be known what elements, are in a compound before a method can be devised for determining exactly how much of each is present.
2. Synthesis is the process of forming a compound from its constituent parts. It is therefore the reverse of analysis. Like analysis, it may be either qualitative or quantitative.
Application of these methods to the determination of the composition of water. The determination of the composition of water is a matter of great interest not only because of the importance of the compound but also because the methods employed illustrate the general methods of analysis and synthesis.
Methods based on analysis. The methods based on analysis may be either qualitative or quantitative in character.
1. Qualitative analysis. As was stated in the study of oxygen, water may be separated into its component parts by means of the electric current. The form of apparatus ordinarily used for effecting this analysis is shown in Fig. 18. A platinum wire, to the end of which is attached a small piece of platinum foil (about 15 mm. by 25 mm.), is fused through each of the tubes B and D, as shown in the figure. The stopcocks at the ends of these tubes are opened and water, to which has been added about one tenth of its volume of sulphuric acid, is poured into the tube A until the side tubes B and D are completely filled. The stopcocks are then closed. The platinum wires extending into the tubes B and D are now connected with the wires leading from two or three dichromate cells joined in series. The pieces of platinum foil within the tubes thus become the electrodes, and the current flows from one to the other through the acidulated water. As soon as the current passes, bubbles of gas rise from each of the electrodes and collect in the upper part of the tubes. The gas rising from the negative electrode is found to be hydrogen, while that from the positive electrode is oxygen. It will be seen that the volume of the hydrogen is approximately double that of the oxygen. Oxygen is more soluble in water than hydrogen, and a very little of it is also lost by being converted into ozone and other substances. It has been found that when the necessary corrections are made for the error due to these facts, the volume of the hydrogen is exactly double that of the oxygen.
Fig. 19 illustrates a simpler form of apparatus, which may be used in place of that shown in Fig. 18. A glass or porcelain dish is partially filled with water to which has been added the proper amount of acid. Two tubes filled with the same liquid are inverted over the electrodes. The gases resulting from the decomposition of the water collect in the tubes.
2. Quantitative analysis. The analysis just described is purely qualitative and simply shows that water contains hydrogen and oxygen. It does not prove the absence of other elements; indeed it does not prove that the hydrogen and oxygen are present in the proportion in which they are liberated by the electric current. The method may be made quantitative, however, by weighing the water decomposed and also the hydrogen and oxygen obtained in its decomposition. If the combined weights of the hydrogen and oxygen exactly equal the weight of the water decomposed, then it would be proved that the water consists of hydrogen and oxygen in the proportion in which they are liberated by the electric current. This experiment is difficult to carry out, however, so that the more accurate methods based on synthesis are used.
Methods based on synthesis. Two steps are necessary to ascertain the exact composition of water by synthesis: (1) to show by qualitative synthesis that water is formed by the union of oxygen with hydrogen; (2) to determine by quantitative synthesis in what proportion the two elements unite to form water. The fact that water is formed by the combination of oxygen with hydrogen was proved in the preceding chapter. The quantitative synthesis may be made as follows:
The combination of the two gases is brought about in a tube called a eudiometer. This is a graduated tube about 60 cm. long and 2 cm. wide, closed at one end (Fig. 20). Near the closed end two platinum wires are fused through the glass, the ends of the wires within the tube being separated by a space of 2 mm or 3 mm. The tube is entirely filled with mercury and inverted in a vessel of the same liquid. Pure hydrogen is passed into the tube until it is about one fourth filled. The volume of the gas is then read off on the scale and reduced to standard conditions. Approximately an equal volume of pure oxygen is then introduced and the volume again read off and reduced to standard conditions. This gives the total volume of the two gases. From this the volume of the oxygen introduced may be determined by subtracting from it the volume of the hydrogen. The combination of the two gases is now brought about by connecting the two platinum wires with an induction coil and passing a spark from one wire to the other. Immediately a slight explosion occurs. The mercury in the tube is at first depressed because of the expansion of the gases due to the heat generated, but at once rebounds, taking the place of the gases which have combined to form water. The volume of the water in the liquid state is so small that it may be disregarded in the calculations. In order that the temperature of the residual gas and the mercury may become uniform, the apparatus is allowed to stand for a few minutes. The volume of the gas is then read off and reduced to standard conditions, so that it may be compared with the volumes of the hydrogen and oxygen originally taken. The residual gas is then tested in order to ascertain whether it is hydrogen or oxygen, experiments having proved that it is never a mixture of the two. From the information thus obtained the composition of the water may be calculated. Thus, suppose the readings were as follows:
Volume of hydrogen taken 20.3 cc. Volume of hydrogen and oxygen 38.7 Volume of oxygen 18.4 Volume of gas left after combination has taken place (oxygen) 8.3
The 20.3 cc. of hydrogen have combined with 18.4 cc. minus 8.3 cc. (or 10.1 cc.) of oxygen; or approximately 2 volumes of hydrogen have combined with 1 of oxygen. Since oxygen is 15.88 times as heavy as hydrogen, the proportion by weight in which the two gases combine is 1 part of hydrogen to 7.94 of oxygen.
Precaution. If the two gases are introduced into the eudiometer in the exact proportions in which they combine, after the combination has taken place the liquid will rise and completely fill the tube. Under these conditions, however, the tube is very likely to be broken by the sudden upward rush of the liquid. Hence in performing the experiment care is taken to introduce an excess of one of the gases. |
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