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B contains a solution of sodium hydroxide, which removes the carbon dioxide formed along with the monoxide. C contains a solution of calcium hydroxide to show that the carbon dioxide is completely removed. E is a hard-glass tube containing 1 or 2 g. of copper oxide, which is heated by a burner. The black copper oxide is reduced to reddish metallic copper by the carbon monoxide, which is thereby changed to carbon dioxide. The presence of the carbon dioxide is shown by the precipitate in the calcium hydroxide solution in D. Any unchanged carbon monoxide is collected over water in F.

Carbon disulphide (CS2). Just as carbon combines with oxygen to form carbon dioxide, so it combines with sulphur to form carbon disulphide (CS2). This compound has been described in the chapter on sulphur.

Hydrocyanic acid (prussic acid)(HCN). Under the proper conditions carbon unites with nitrogen and hydrogen to form the acid HCN, called hydrocyanic acid. It is a weak, volatile acid, and is therefore easily prepared by treating its salts with sulphuric acid:

KCN + H2SO4 = KHSO4 + HCN.

It is most familiar as a gas, though it condenses to a colorless liquid boiling at 26Β°. It has a peculiar odor, suggesting bitter almonds, and is extremely poisonous either when inhaled or when taken into the stomach. A single drop may cause death. It dissolves readily in water, its solution being commonly called prussic acid.

The salts of hydrocyanic acid are called cyanides, the cyanides of sodium and potassium being the best known. These are white solids and are extremely poisonous.

Solutions of potassium cyanide are alkaline. A solution of potassium cyanide turns red litmus blue, and must therefore contain hydroxyl ions. The presence of these ions is accounted for in the following way.

Although water is so little dissociated into its ions H+ and OH- that for most purposes we may neglect the dissociation, it is nevertheless measurably dissociated. Hydrocyanic acid is one of the weakest of acids, and dissociates to an extremely slight extent. When a cyanide such as potassium cyanide dissolves it freely dissociates, and the CN- ions must come to an equilibrium with the H+ ions derived from the water:

H+ + CN- <--> HCN.

The result of this equilibrium is that quite a number of H+ ions from the water are converted into undissociated HCN molecules. But for every H+ ion so removed an OH- ion remains free, and this will give the solution alkaline properties.

EXERCISES

1. How can you prove that the composition of the different allotropic forms of carbon is the same?

2. Are lampblack and bone black allotropic forms of carbon? Will equal amounts of heat be liberated in the combustion of 1 g. of each?

3. How could you judge of the relative purity of different forms of carbon?

4. Apart from its color, why should carbon be useful in the preparation of inks and paints?

5. Could asbestos fibers be used to replace the wire in a safety lamp?

6. Why do most acids decompose carbonates?

7. What effect would doubling the pressure have upon the solubility of carbon dioxide in water?

8. What compound would be formed by passing carbon dioxide into a solution of ammonium hydroxide? Write the equation.

9. Write equations for the preparation of K2CO3; of BaCO3; of MgCO3.

10. In what respects are carbonic and sulphurous acids similar?

11. Give three reasons why the reaction which takes place when a solution of calcium acid carbonate is heated, completes itself.

12. How could you distinguish between carbonates and sulphites?

13. How could you distinguish between oxygen, hydrogen, nitrogen, nitrous oxide, and carbon dioxide?

14. Could a solution of sodium hydroxide be substituted for the solution of calcium hydroxide in testing for carbon dioxide?

15. What weight of sodium hydroxide is necessary to neutralize the carbonic acid formed by the action of hydrochloric acid on 100 g. of calcium carbonate?

16. What weight of calcium carbonate would be necessary to prepare sufficient carbon dioxide to saturate 10 l. of water at 15Β° and under ordinary pressure?

17. On the supposition that calcium carbide costs 12 cents a kilogram, what would be the cost of an amount sufficient to generate 100 l. of acetylene measured at 20Β° and 740 mm.?

18. How would the volume of a definite amount of carbon monoxide compare with the volume of carbon dioxide formed by its combustion, the measurements being made under the same conditions?

CHAPTER XVIII FLAMES,β€”ILLUMINANTS

Conditions necessary for flames. It has been seen that when two substances unite chemically, with the production of light and heat, the act of union is called combustion. When one of the substances undergoing combustion remains solid at the temperature occasioned by the combustion, light may be given off, but there is no flame. Thus iron wire burning in oxygen throws off a shower of sparks and is brilliantly incandescent, but no flame is seen. When, however, both of the substances are gases or vapors at the temperature reached in the combustion, the act of union is accompanied by a flame.

Flames from burning liquids or solids. Many substances which are liquids or solids at ordinary temperatures burn with a flame because the heat of combustion vaporizes them slowly, and the flame is due to the union of this vapor with the gas supporting the combustion.

Supporter of combustion. That gas which surrounds the flame and constitutes the atmosphere in which the combustion occurs is said to support the combustion. The other gas which issues into this atmosphere is said to be the combustible gas. Thus, in the ordinary combustion of coal gas in the air the coal gas is said to be combustible, while the air is regarded as the supporter of combustion. These terms are entirely relative, however, for a jet of air issuing into an atmosphere of coal gas will burn when ignited, the coal gas supporting the combustion. Ordinarily, when we say that a gas is combustible we mean that it is combustible in an atmosphere of air.

Fig. 62 Fig. 62

Either gas may be the supporter of combustion. That the terms combustible and supporter of combustion are merely relative may be shown in the following way: A lamp chimney A is fitted with a cork and glass tubes, as shown in Fig. 62. The tube C should have a diameter of from 12 to 15 mm. A thin sheet of asbestos in which is cut a circular opening about 2 cm. in diameter is placed over the top of the chimney. The opening in the asbestos is closed with the palm of the hand, and gas is admitted to the chimney through the tube B. The air in the chimney is soon expelled through the tube C, and the gas itself is then lighted at the lower end of this tube. The hand is now removed from the opening in the asbestos, when the flame at the end of the tube at once rises and appears at the end within the chimney, as shown in the figure. The excess of coal gas now escapes from the opening in the asbestos and may be lighted. The flame at the top of the asbestos board is due to the combustion of coal gas in air, while the flame within the chimney is due to the combustion of air in coal gas, the air being drawn up through the tube by the escaping gas.

Appearance of flames. The flame caused by the union of hydrogen and oxygen is almost colorless and invisible. Chlorine and hydrogen combine with a pale violet flame, carbon monoxide burns in oxygen with a blue flame, while ammonia burns with a deep yellow flame. The color and appearance of flames are therefore often quite characteristic of the particular combustion which occasions them.

Structure of flames. When the gas undergoing combustion issues from a round opening into an atmosphere of the gas supporting combustion, as is the case with the burning Bunsen burner (Fig. 63), the flame is generally conical in outline. It consists of several distinct cones, one within the other, the boundary between them being marked by differences of color or luminosity. In the simplest flame, of which hydrogen burning in oxygen is a good example, these cones are two in number,β€”an inner one, formed by unburned gas, and an outer one, usually more or less luminous, consisting of the combining gases. This outer one is in turn surrounded by a third envelope of the products of combustion; this envelope is sometimes invisible, as in the present case, but is sometimes faintly luminous. The lower part of the inner cone of the flame is quite cool and consists of unburned gas. Toward the top of the inner cone the gas has become heated to a high temperature by the burning envelope surrounding it. On reaching the supporter of combustion on the outside it is far above its kindling temperature, and combustion follows with the evolution of much heat. The region of combustion just outside the inner cone is therefore the hottest part of the flame.

Fig. 63 Fig. 63

Oxidizing and reducing flames. Since the tip of the outside cone consists of very hot products of combustion mixed with oxygen from the air, a substance capable of oxidation placed in this part of the flame becomes very hot and is easily oxidized. The oxygen with which it combines comes, of course, from the atmosphere, and not from the products of combustion. This outer tip of the flame is called the oxidizing flame.

At the tip of the inner cone the conditions are quite different. This region consists of a highly heated combustible gas, which has not yet reached a supply of oxygen.

If a substance rich in oxygen, such as a metallic oxide, is placed in this region of the flame, the heated gases combine with its oxygen and the substance is reduced. This part of the flame is called the reducing flame. These flames are used in testing certain substances, especially minerals. For this purpose they are produced by blowing into a small luminous Bunsen flame from one side through a blowpipe. This is a tube of the shape shown in Fig. 64. The flame is directed in any desired way and has the oxidizing and reducing regions very clearly marked (Fig. 65). It is non-luminous from the same causes which render the open Bunsen burner flame non-luminous, the gases from the lungs serving to furnish oxygen and to dilute the combustible gas.

Fig. 64 Fig. 64
Fig. 65 Fig. 65

Luminosity of flames. The luminosity of flames is due to a number of distinct causes, and may therefore be increased or diminished in several ways.

1. Presence of solid matter. The most obvious of these causes is the presence in the flame of incandescent solid matter. Thus chalk dust sifted into a non-luminous flame renders it luminous. When hydrocarbons form a part of the combustible gas, as they do in nearly all illuminating gases and oils, some carbon is usually set free in the process of combustion. This is made very hot by the flame and becomes incandescent, giving out light. In a well-regulated flame it is afterward burned up, but when the supply of oxygen is insufficient it escapes from the flame as lampblack or soot. That it is temporarily present in a well-burning luminous flame may be demonstrated by holding a cold object, such as a small evaporating dish, in the flame for a few seconds. This cold object cools the carbon below its kindling temperature, and it is deposited on the object as soot.

2. Pressure. A second factor in the luminosity of flames is the pressure under which the gases are burning. Under increased pressure there is more matter in a given volume of a gas, and the chemical action is more energetic than when the gases are

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