The family. The four elements named in the above table form a strongly marked family of elements and illustrate very clearly the way in which the members of a family in a periodic group resemble each other, as well as the character of the differences which we may expect to find between the individual members.
1. Occurrence. These elements do not occur in nature in the free state. The compounds of the last three elements of the family are found extensively in sea water, and on this account the name halogens, signifying "producers of sea salt," is sometimes applied to the family.
2. Properties. As will be seen by reference to the table, the melting points and boiling points of the elements of the family increase with their atomic weights. A somewhat similar gradation is noted in their color and state. One atom of each of the elements combines with one atom of hydrogen to form acids, which are gases very soluble in water. The affinity of the elements for hydrogen is in[Pg 175] the inverse order of their atomic weights, fluorine having the strongest affinity and iodine the weakest. Only chlorine and iodine form oxides, and those of the former element are very unstable. The elements of the group are univalent in their compounds with hydrogen and the metals.
FLUORINE
Occurrence. The element fluorine occurs in nature most abundantly as the mineral fluorspar (CaF2), as cryolite (Na3AlF6), and in the complex mineral apatite (3 Ca3(PO4)2·CaF2).
Preparation. All attempts to isolate the element resulted in failure until recent years. Methods similar to those which succeed in the preparation of the other elements of the family cannot be used; for as soon as the fluorine is liberated it combines with the materials of which the apparatus is made or with the hydrogen of the water which is always present. The preparation of fluorine was finally accomplished by the French chemist Moissan by the electrolysis of hydrofluoric acid. Perfectly dry hydrofluoric acid (HF) was condensed to a liquid and placed in a U-shaped tube made of platinum (or copper), which was furnished with electrodes and delivery tubes, as shown in Fig. 52. This liquid is not an electrolyte, but becomes such when potassium fluoride is dissolved in it. When this solution was electrolyzed hydrogen was set free at the cathode and fluorine at the anode.
Properties. Fluorine is a gas of slightly yellowish color, and can be condensed to a liquid boiling at -187° under atmospheric pressure. It solidifies at -223°. It is extremely active chemically, being the most active of all the elements at ordinary temperatures.
It combines with all the common elements save oxygen, very often with incandescence and the liberation of much heat. It has a strong affinity for hydrogen and is able to withdraw it from its compounds with other elements. Because of its great activity it is extremely poisonous. Fluorine does not form any oxides, neither does it form any oxygen acids, in which respects it differs from the other members of the family.
Hydrofluoric acid (HF). Hydrofluoric acid is readily obtained from fluorspar by the action of concentrated sulphuric acid. The equation is
CaF2 + H2SO4 = CaSO4 + 2HF.
In its physical properties it resembles the binary acids of the other elements of this family, being, however, more easily condensed to a liquid. The anhydrous acid boils at 19° and can therefore be prepared at ordinary pressures. It is soluble in all proportions in water, and a concentrated solution—about 50%—is prepared for the market. Its fumes are exceedingly irritating to the respiratory organs, and several chemists have lost their lives by accidentally breathing them.
HENRI MOISSAN (French) (1853-1907)
Famous for his work with the electric furnace at high temperatures; prepared artificial diamonds, together with many new binary compounds such as carbides, silicides, borides, and nitrides; isolated fluorine and studied its properties and its compounds very thoroughly
Famous for his work with the electric furnace at high temperatures; prepared artificial diamonds, together with many new binary compounds such as carbides, silicides, borides, and nitrides; isolated fluorine and studied its properties and its compounds very thoroughly
Chemical properties. Hydrofluoric acid, like other strong acids, readily acts on bases and metallic oxides and forms the corresponding fluorides. It also dissolves certain metals such as silver and copper. It acts very vigorously upon organic matter, a single drop of the concentrated acid making a sore on the skin which is very painful and slow in healing. Its most characteristic property is its action upon silicon dioxide (SiO2), with which it forms water and the gas silicon tetrafluoride (SiF4), as shown in the equation
SiO2 + 4HF = SiF4 + 2H2O.
Glass consists of certain compounds of silicon, which are likewise acted on by the acid so that it cannot be kept in glass bottles. It is preserved in flasks made of wax or gutta-percha.
Etching. Advantage is taken of this reaction in etching designs upon glass. The glass vessel is painted over with a protective paint upon which the acid will not act, the parts which it is desired to make opaque being left unprotected. A mixture of fluorspar and sulphuric acid is then painted over the vessel and after a few minutes the vessel is washed clean. Wherever the hydrofluoric acid comes in contact with the glass it acts upon it, destroying its luster and making it opaque, so that the exposed design will be etched upon the clear glass. Frosted glass globes are often made in this way.
The etching may also be effected by covering the glass with a thin layer of paraffin, cutting the design through the wax and then exposing the glass to the fumes of the acid.
Salts of hydrofluoric acid,—fluorides. A number of the fluorides are known, but only one of them, calcium fluoride (CaF2), is of importance. This is the well-known mineral fluorspar.
CHLORINE
Historical. While studying the action of hydrochloric acid upon the mineral pyrolusite, in 1774, Scheele obtained a yellowish, gaseous substance to which he gave a name in keeping with the phlogiston theory then current. Later it was supposed to be a compound containing oxygen. In[Pg 178] 1810, however, the English chemist Sir Humphry Davy proved it to be an element and named it chlorine.
Occurrence. Chlorine does not occur free in nature, but its compounds are widely distributed. For the most part it occurs in combination with the metals in the form of chlorides, those of sodium, potassium, and magnesium being most abundant. Nearly all salt water contains these substances, particularly sodium chloride, and very large salt beds consisting of chlorides are found in many parts of the world.
Preparation. Two general methods of preparing chlorine may be mentioned, namely, the laboratory method and the electrolytic method.
1. Laboratory method. In the laboratory chlorine is made by warming the mineral pyrolusite (manganese dioxide, MnO2) with concentrated hydrochloric acid. The first reaction, which seems to be similar to the action of acids upon oxides in general, is expressed in the equation
MnO2 + 4HCl = MnCl4 + 2H2O.
The manganese compound so formed is very unstable, however, and breaks clown according to the equation
MnCl4 = MnCl2 + 2Cl.
Instead of using hydrochloric acid in the preparation of chlorine it will serve just as well to use a mixture of sodium chloride and sulphuric acid, since these two react to form hydrochloric acid. The following equations will then express the changes:
(1) 2NaCl + H2SO4 = Na2SO4 + 2HCl.
(2) MnO2 + 4 HCl = MnCl2 + 2Cl + 2H2O.
(3) MnCl2 + H2SO4 = MnSO4 + 2HCl.
Combining these equations, the following equation expressing the complete reaction is obtained:
2NaCl + MnO2 + 2H2SO4 = MnSO4 + Na2SO4 + 2H2O + 2Cl.
Since the hydrochloric acid liberated in the third equation is free to act upon manganese dioxide, it will be seen that all of the chlorine originally present in the sodium chloride is set free.
The manganese dioxide and the hydrochloric acid are brought together in a flask, as represented in Fig. 53, and a gentle heat is applied. The rate of evolution of the gas is regulated by the amount of heat applied, and the gas is collected by displacement of air. As the equations show, only half of the chlorine present in the hydrochloric acid is liberated.
2. Electrolytic method. Under the discussion of electrolysis (p. 102) it was shown that when a solution of sodium chloride is electrolyzed chlorine is evolved at the anode, while the sodium set free at the cathode reacts with the water to form hydrogen, which is evolved, and sodium hydroxide, which remains in solution. A great deal of the chlorine required in the chemical industries is now made in this way in connection with the manufacture of sodium hydroxide.
Physical properties. Chlorine is a greenish-yellow gas, which has a peculiar suffocating odor and produces a very violent effect upon the throat and lungs. Even when inhaled in small quantities it often produces all the symptoms of a[Pg 180] hard cold, and in larger quantities may have serious and even fatal action. It is quite heavy (density = 2.45) and can therefore be collected by displacement of air. One volume of water under ordinary conditions dissolves about three volumes of chlorine. The gas is readily liquefied, a pressure of six atmospheres serving to liquefy it at 0°. It forms a yellowish liquid which solidifies at -102°.
Chemical properties. At ordinary temperatures chlorine is far more active chemically than any of the elements we have so far considered, with the exception of fluorine; indeed, it is one of the most active of all elements.
1. Action on metals. A great many metals combine directly with chlorine, especially when hot. A strip of copper foil heated in a burner flame and then dropped into chlorine burns with incandescence. Sodium burns brilliantly when heated strongly in slightly moist chlorine. Gold and silver are quickly tarnished by the gas.
2. Action on non-metals. Chlorine has likewise a strong affinity for many of the non-metals. Thus phosphorus burns in a current of the gas, while antimony and arsenic in the form of a fine powder at once burst into flame when dropped into jars of the gas. The products formed in all cases where chlorine combines with another element are called chlorides.
3. Action on hydrogen. Chlorine has a strong affinity for hydrogen, uniting with it to form hydrochloric acid. A jet of hydrogen burning in the air continues to burn when introduced into a jar of chlorine, giving a somewhat luminous flame. A mixture of the two gases explodes violently when a spark is passed through it or when it is exposed to bright sunlight. In the latter case it is the light and not the heat which starts the action.[Pg 181]
4. Action on substances containing hydrogen. Not only will chlorine combine directly with free hydrogen but it will often abstract the element from its compounds. Thus, when chlorine is passed into a solution containing hydrosulphuric acid, sulphur is precipitated and Hydrochloric acid formed. The reaction is shown by the following equation:
H2S + 2Cl = 2HCl + S.
With ammonia the action is similar:
NH3 + 3Cl = 3HCl + N.
The same tendency is very strikingly seen in the action of chlorine upon turpentine. The latter substance is largely made up of compounds having the composition represented by the formula C10H16. When a strip of paper moistened with warm turpentine is placed in a jar of chlorine dense fumes of hydrochloric acid appear and a black deposit of carbon is formed. Even water, which is a very stable compound, can be decomposed by chlorine, the oxygen being liberated. This may be shown in the following way:
If a long tube of rather large diameter is filled with a strong solution of chlorine in water and inverted in a vessel of the same solution, as shown in Fig. 54, and the apparatus is placed in bright sunlight, very soon bubbles of a gas will be observed to rise through the solution and collect in the tube. An examination of this gas will show that it is oxygen. It is liberated from water in accordance with the following equation:
H2O + 2Cl = 2HCl + O.
5. Action on color substances,—bleaching action. If strips of brightly colored cloth or some highly colored flowers are placed in quite dry chlorine, no marked change[Pg 182] in color is noticed as a rule. If, however, the cloth and flowers are first moistened, the color rapidly disappears, that is, the objects are bleached. Evidently the moisture as well as the chlorine is concerned in the action, and a study of the case shows that the chlorine has combined with the hydrogen of the water. The oxygen set free oxidizes the color substance, converting it into a colorless compound. It is evident from this explanation that chlorine will only bleach those substances which are changed into colorless compounds by oxidation.
6. Action as a disinfectant. Chlorine has also marked germicidal properties, and the free element, as well as compounds from which it is easily liberated, are used as disinfectants.
Nascent state. It will be noticed that oxygen when set free from water by chlorine is able to do what ordinary oxygen cannot do, for both the cloth and the flowers are unchanged in the air which contains oxygen. It is generally true that the activity of an element is greatest at the instant of liberation from its compounds. To express this fact elements at the instant of liberation are said to be in the nascent state. It is nascent oxygen which does the bleaching.
Hydrochloric acid (muriatic acid) (HCl). The preparation of hydrochloric acid may be discussed under two general heads:
1. Laboratory preparation. The product formed by the burning of hydrogen in chlorine is the gas hydrochloric acid. This substance is much more easily obtained, however, by treating common salt (sodium chloride) with sulphuric acid. The following equation shows the reaction:
2NaCl + H2SO4 = Na2SO4 + 2HCl.
The dry salt is placed in a flask furnished with a funnel tube and an exit tube, the sulphuric acid is added, and the flask gently warmed. The hydrochloric acid gas is rapidly given off and can be collected by displacement of air. The same apparatus can be used as was employed in the preparation of chlorine (Fig. 53).
When a solution of salt is treated with sulphuric acid there is no very marked action. The hydrochloric acid formed is very soluble in water, and so does not escape from the solution; hence a state of equilibrium is soon reached between the four substances represented in the equation. When concentrated sulphuric acid, in which hydrochloric acid is not soluble, is poured upon dry salt the reaction is complete.
2. Commercial preparation. Commercially, hydrochloric acid is prepared in connection with the manufacture of sodium sulphate, the reaction being the same as that just given. The reaction is carried out in a furnace, and the hydrochloric acid as it escapes in the form of gas is passed into water in which it dissolves, the solution forming the hydrochloric acid of commerce. When the materials are pure a colorless solution is obtained. The most concentrated solution has a density of 1.2 and contains 40% HCl. The commercial acid, often called muriatic acid, is usually colored yellow by impurities.
Composition of hydrochloric acid. When a solution of hydrochloric acid is electrolyzed in an apparatus similar to the one in which water was electrolyzed (Fig. 18), chlorine collects at the anode and hydrogen at the cathode. At first the chlorine dissolves in the water, but soon the water in the one tube becomes saturated with it, and if the stopcocks are left open until this is the case, and are then closed, it will be seen that the two gases are set free in equal volumes.[Pg 184]
When measured volumes of the two gases are caused to unite it is found that one volume of hydrogen combines with one of chlorine. Other experiments show that the volume of hydrochloric acid formed is just equal to the sum of the volumes of hydrogen and chlorine. Therefore one volume of hydrogen combines with one volume of chlorine to form two volumes of hydrochloric acid gas. Since chlorine is 35.18 times as heavy as hydrogen, it follows that one part of hydrogen by weight combines with 35.18 parts of chlorine to form 36.18 parts of hydrochloric acid.
Physical properties. Hydrochloric acid is a colorless gas which has an irritating effect when inhaled, and possesses a sour, biting taste, but no marked odor. It is heavier than air (density = 1.26) and is very soluble in water. Under standard conditions 1 volume of water dissolves about 500 volumes of the gas. On warming such a solution the gas escapes, until at the boiling point the solution contains about 20% by weight of HCl. Further boiling will not drive out any more acid, but the solution will distill with unchanged concentration. A more dilute solution than this will lose water on boiling until it has reached the same concentration, 20%, and will then distill unchanged. Under high pressure the gas can be liquefied, 28 atmospheres being required at 0°. Under these conditions it forms a colorless liquid which is not very active chemically. It boils at -80° and solidifies at -113°. The solution of the gas in water is used almost entirely in the place of the gas itself, since it is not only far more convenient but also more active.
Chemical properties. The most important chemical properties of hydrochloric acid are the following:
1. Action as an acid. In aqueous solution hydrochloric acid has very strong acid properties; indeed, it is one of[Pg 185] the strongest acids. It acts upon oxides and hydroxides, converting them into salts:
NaOH + HCl = NaCl + H2O, CuO + 2HCl = CuCl2 + H2O.
It acts upon many metals, forming chlorides and liberating hydrogen:
Zn + 2HCl = ZnCl2 + 2H, Al + 3HCl = AlCl3 + 3H.
Unlike nitric and sulphuric acids it has no oxidizing action, so that when it acts on metals hydrogen is always given off.
2. Relation to combustion. Hydrochloric acid gas is not readily decomposed, and is therefore neither combustible nor a supporter of combustion.
3. Action on oxidizing agents. Although hydrochloric acid is incombustible, it can be oxidized under some circumstances, in which case the hydrogen combines with oxygen, while the chlorine is set free. Thus, when a solution of hydrochloric acid acts upon manganese dioxide part of the chlorine is set free:
MnO2 + 4HCl = MnCl2 + 2H2O + 2Cl.
Aqua regia. It has been seen that when nitric acid acts as an oxidizing agent it usually decomposes, as represented in the equation
2HNO3 = H2O + 2NO + 3O.
The oxygen so set free may act on hydrochloric acid:
6HCl + 3O = 3H2O + 6Cl.
The complete equation therefore is
2HNO3 + 6HCl = 4H2O + 2NO + 6Cl.
When concentrated nitric and hydrochloric acids are mixed this reaction goes on slowly, chlorine and some other substances not represented in the equation being formed. The mixture is known as aqua regia and is commonly prepared by adding one volume of nitric acid to three volumes of hydrochloric acid. It acts more powerfully upon metals and other substances than either of the acids separately, and owes its strength not to acid properties but to the action of the nascent chlorine which it liberates. Consequently, when it acts upon metals such as gold it converts them into chlorides, and the reaction can be represented by such equations as
Au + 3Cl = AuCl3.
Salts of hydrochloric acid,—chlorides. The chlorides of all the metals are known and many of them are very important compounds. Some of them are found in nature, and all can be prepared by the general method of preparing salts. Silver chloride, lead chloride, and mercurous chloride are insoluble in water and acids, and can be prepared by adding hydrochloric acid to solutions of compounds of the respective elements. While the chlorides have formulas similar to the fluorides, their properties are often quite different. This is seen in the solubility of the salts. Those metals whose chlorides are insoluble form soluble fluorides, while many of the metals which form soluble chlorides form insoluble fluorides.
Compounds of chlorine with oxygen and hydrogen. Chlorine combines with oxygen and hydrogen to form four different acids. They are all quite unstable, and most of them cannot be prepared in pure form; their salts can easily be made, however, and some of them will be met with in the[Pg 187] study of the metals. The formulas and names of these acids are as follows:
| HClO | hypochlorous acid. |
| HClO2 | chlorous acid. |
| HClO3 | chloric acid. |
| HClO4 | perchloric acid. |
Oxides of chlorine. Two oxides are known, having the formulas Cl2O and ClO2. They decompose very easily and are good oxidizing agents.
BROMINE
Historical. Bromine was discovered in 1826 by the French chemist Ballard, who isolated it from sea salt. He named it bromine (stench) because of its unbearable fumes.
Occurrence. Bromine occurs almost entirely in the form of bromides, especially as sodium bromide and magnesium bromide, which are found in many salt springs and salt deposits. The Stassfurt deposits in Germany and the salt waters of Ohio and Michigan are especially rich in bromides.
Preparation of bromine. The laboratory method of preparing bromine is essentially different from the commercial method.
