An Introduction to Chemical Science Part 9

85. Preparation. Experiment 52.--To 10 g. KNO3 or NaNO3, in a flask, add 15 cc. H2SO4. Securely fasten the cork of the d.t., as HNO3 is likely to loosen it, and pa.s.s the other end to the bottom of a t.t. held deep in a bottle of water (Fig. 26). Apply heat, and collect 4 or 5 cc.of the liquid. The usual reaction is: KNO3 + H2SO4 = HKSO4 + HNO3. With greater heat, 2 KNO3 + H2SO4 = K2SO4 + 2HNO3. Which is most economical of KNO3? Of H2SO4? Instead of a flask, a t.t. may be used if desired (Fig. 27).

86. Properties and Tests.

Experiment 53.--(1) Note the color of the prepared liquid. (2) Put a drop on the finger; then wash it off at once. (3) Dip a quill or piece of white silk into it; then wash off the acid.

What color is imparted to animal substances? (4) Add a little to a few bits of Cu turnings, or to a Cu coin. Write the equation.

(5) To 2 cc.indigo solution, add 2 cc. HNO3. State the leading properties of HNO3, from these tests.

87. Chemically Pure HNO3 is a Colorless Liquid.-- The yellow color of that prepared in Experiment 52 is due to liquid NO2 dissolved in it. It is then called fuming HNO3, and is very strong. NO2 is formed at a high temperature.

Commercial or ordinary HNO3, is made from NaNO3, this being cheaper than KNO3; it is about half water.

88. Uses. HNO3 is the basis of many nitrates, as AgNO3, used for photography, Ba(NO3)2 and Sr(NO3)2 for fire-works, and others for dyeing and printing calico; it is employed in making aqua regia, sulphuric acid, nitro-glycerine, gun-cotton, aniline colors, zylonite, etc.

Enough experiments have been performed to answer the question whether some acids can be prepared from their salts. H2SO4 is not so made, because no acid is strong enough to act on its salts. In making HCl, HNO3, etc., sulphuric acid was used, being the strongest.

AQUA REGIA.

89. Preparation and Action. Experiment 54.--Into a t.t. put 2 cc.

HNO3, and 14 qcm. of either Au leaf or Pt. Warm in a flame. If the metal is pure, no action takes place. Into another tube put 6 cc. HCl and add a similar leaf. Heat this also. There should be no action. Pour the contents of one t.t. into the other. Note the effect. Which is stronger, one of the acids, or the combination of the two? Note the odor. It is that of Cl. 3HCl + HNO3 = NOCl + 2H2O + Cl2. This reaction is approximate only. The strength is owing to nascent chlorine, which unites with Au. Au + 3Cl = AuCl3. If Pt be used, PtCl4 is produced. No other acid except nitro-hydrochloric will dissolve Au or Pt; hence the ancients called it aqua regia, or king of liquids. It must be made as wanted, since it cannot be kept and retain its strength.

CHAPTER XIX.

SULPHURIC ACID.

90. Preparation.

Experiment 55.--Having fitted a cork with four or five perforations to a large t.t., pa.s.s a d.t. from three of these to three smaller t.t., leaving the others open to the air, as in Figure 28. Into one t.t. put 5 cc. H2O, into another 5 g. Cu turnings and 10 cc. H2SO4, into the third 5 g. Cu turnings and 10 cc. dilute HNO3, half water. Hang on a ring stand, and slowly heat the tubes containing H2O and H2SO4. Notice the fumes that pa.s.s into the large t.t.

Trace out and apply to Figure 28 these reactions:--

(1) Cu + 2 H2SO4 = CuSO4 + 2 H2O + SO2.

(2) 3 Cu + 8 HNO3 = 3 Cu(NO3)2+ 4 H2O + 2 NO.

(3) NO + O = NO2.

(4) SO2 + H2O + NO2 =H2SO4 + NO.

(4) comes from combining the gaseous products in (1), (2), (3).

In (3), NO takes an atom of O from the air, becoming NO2, and at once gives it up, to the H2SO3 (H2O + SO2), making H2SO4, and again goes through the same operation of taking up O and pa.s.sing it along. NO is thus called a carrier of O. It is a reducing agent, while NO2 is an oxidizing agent. This is a continuous process, and very important, since it changes useless H2SO3 into valuable H2SO4. If exposed to the air, H2SO3 would very slowly take up O and become H2SO4.

Instead of the last experiment, this may be employed if preferred: Burn a little S in a receiver. Put into an evaporating-dish, 5 cc. HNO3, and dip a paper or piece of cloth into it. Hang the paper in the receiver of SO2, letting no HNO3 drop from it. Continue this operation till a small quant.i.ty of liquid is found in the bottle. The fumes show that HNO3 has lost O. 2 HNO3 + SO2 = H2SO4 + 2 NO2.

91. Tests for H2SO4.

Experiment 56.--(1) Test the liquid with litmus. (2) Transfer it to a t.t., and add an equal volume of BaCl2 solution. H2SO4 + BaCl2 = ? Is BaSO4 soluble? (3) Put one drop H2SO4 from the reagent bottle in 10 cc. H2O in a clean t.t., and add 1 cc. BaCl2 solution. Look for any cloudiness. This is the characteristic test for H2SO4 and soluble sulphates, and so delicate that one drop in a liter of H2O can be detected. (4) Instead of H2SO4, try a little Na2SO4 solution. (5) Put two or three drops of strong H2SO4 on writing-paper, and evaporate, high over a flame, so as not to burn the paper. Examine it when dry. (6) Put a stick into a t.t. containing 2 cc. H2SO4, and note the effect. (7) Review Experiment 5. (8) Into an e.d. pour 5 cc. H2O, and then 15 cc.

H2SO4. Stir it meantime with a small t.t. containing 2 or 3 cc.

NH4OH, and notice what takes place in the latter; also note the heat of the e.d.

The effects of (5), (6), (7), and (8) are due to the intense affinity which H2SO4 has for H2O. So thirsty is it that it even abstracts H and O from oxalic acid in the right proportion to form H2O, combines them, and then absorbs the water.

92. Affinity for Water.--This acid is a desiccator or dryer, and is used to take moisture from the air and prevent metallic substances from rusting. In this way it dilutes itself, and may increase its weight threefold. In diluting, the acid must always be poured into the water slowly and with stirring, not water into the acid, since, as H2O is lighter than H2SO4, heat enough may be set free at the surface of contact to cause an explosion.

Contraction also takes place, as may be shown by accurately measuring each liquid in a graduate, before mixing, and again when cold. The mixture occupies less volume than the sum of the two volumes. For the best results the volume of the acid should be about three times that of the water.

93. Sulphuric Acid made on a Large Scale involves the same principles as shown in Experiment 55, excepting that S02 is obtained by burning S or roasting FeS2 (pyrite),

[Fig. 29.]

and HNO3 is made on the spot from NaNO3 and H2SO4. SO2 enters a large leaden chamber, often 100 to 300 feet long, and jets of steam and small portions of HNO3 are also forced in. The "chamber acid" thus formed is very dilute, and must be evaporated first in leaden pans, and finally in gla.s.s or platinum retorts, since strong H2SO4, especially if hot, dissolves lead. See Experiment 124. Study Figure 29, and write the reactions. 2 HNO3 breaks up into 2 NO2, H2O, and O. 94. Importance.--Sulphuric acid has been called, next to human food, the most indispensable article known.

There is hardly a product of modern civilization in the manufacture of which it is not directly or indirectly used.

Nearly a million tons are made yearly in Great Britain alone. It is the basis of all acids, as Na2CO3 is of alkalies. It is the life of chemical industry, and the quant.i.ty of it consumed is an index of a people's civilization. Only a few of its uses can be stated here. The two leading ones are the reduction of Ca3(PO4)2 for artificial manures and the sodium carbonate manufacture.

Foods depend on the productiveness of soils and on fertilizers, and thus indirectly our daily bread is supplied by means of this acid; and from sodium carbonate gla.s.s, soap, saleratus, baking- powders, and most alkalies are made directly or indirectly. H2SO4 is employed in bleaching, dyeing, printing, telegraphy, electroplating, galvanizing iron and wire, cleaning metals, refining Au and Ag, making alum, blacking, vitriols, glucose, mineral waters, ether, indigo, madder, nitroglycerine, gun- cotton, parchment, celluloid, etc., etc.

FUMING SULPHURIC ACID.

95. Nordhausen or Fuming Sulphuric Acid, H2S207 used in dissolving indigo and preparing coal-tar pigments, is made by distilling FeSO4. 4FeSO4 + H2O = H2S207 + 2Fe203 + 2S02. This was the original sulphuric acid. It is also formed when S03 is dissolved in H2SO4. When exposed to the air, S03 escapes with fuming.

CHAPTER XX.

AMMONIUM HYDRATE.

96. Preparation of Bases.--We have seen that many acids are made by acting on a salt of the acid required, with a stronger acid.

This is the direct way. The following experiments will show that bases may be prepared in a similar way by acting on salts of the base required with other bases, which we may regard as stronger than the ones to be obtained.

97. Preparation of NH4OH and NH3.

Experiment 57.--Powder 10 g. ammonium chloride, NH4Cl, in a mortar and mix with 10 g. calcium hydrate, Ca(OH)2; recently slaked lime is the best. Cover with water in a flask, and connect with Woulff bottles, as for making HCl (Fig. 22); heat the flask for fifteen minutes or more. The experiment may be tried on a smaller scale with a t.t. if desired.

The reaction is: 2NH4Cl + Ca(OH)2 = CaCl2 + 2NH4OH. NH4OH is broken up into NH3, ammonia gas, and water. NH4OH = NH3 + H2O.

These pa.s.s over into the first bottle, where the water takes up the NH3, for which it has great affinity. One volume of water at 0 will absorb more than 1000 volumes of NH3. Thus NH4OH may be called a solution of NH3, in H2O. Write the reaction.

Experiment 58.--Powder and mix 2 or 3 g. each of ammonium nitrate, NH4NO3, and Ca(OH)2; put them into a t.t., and heat slowly. Note the odor. 2NH4NO3 + Ca(OH)2 = ?

98. Tests.

Experiment 59.--(1) Generate a little of the gas in a t.t., and note the odor. (2) Test the gas with wet red litmus paper. (3) Put a little HCl into an e.d., and pa.s.s over it the fumes of NH3 from a d.t. Note the result, and write the equation. (4) Fill a small t.t. with the gas by upward displacement; then, while still inverted, put the mouth of the t.t. into water. Explain the rise of the water. (5) How might NH4Cl be obtained from the NH4OH in the Woulff bottles? (6) Test the liquid in each bottle with red litmus paper. (7) Add some from the first bottle to 5 or 10 cc.

of a solution of FeSO4 or FeCl2, and look for a ppt. State the reaction.

99. Formation.--Ammonia, hartshorn, exists in animal and vegetable compounds, in salts, and, in small quant.i.ties, in the atmosphere. Rain washes it from the atmosphere into the soil; plants take it from the soil; animals extract it from plants.

Coal, bones, horns, etc., are the chief sources of it, and from them it is obtained by distillation. It results also from decomposing animal matter. NH3 can be produced by the direct union of N and H, only by an electric discharge or by ozone. It may be collected over Hg like other gases that are very soluble in water.

100. Uses. --Ammonium hydrate, NH4OH, and ammonia, NH3, are used in chemical operations, in making artificial ice, and to some extent in medicine; from them also may be obtained ammonium salts. State what you would put with NH4OH to obtain (NH4)2SO4.

To obtain NH4NO3. The use of NH4OH in the laboratory may be ill.u.s.trated by the following experiment:--

Experiment 60.--Into a t.t. put 10 cc. of a solution of ferrous sulphate, FeSO4. Into another put 10 cc. of sodium sulphate solution, Na2SO4. Add a little NH4OH to each. Notice a ppt. in the one case but none in the other. If solutions of these two compounds were mixed, the metals Fe and Na could be separated by the addition of NH4OH, similar to the separation of Ag and Cu by HCl. Try the experiment.

CHAPTER XXI.

SODIUM HYDRATE.