ACIDS, BASES, AND SALTS; NEUTRALIZATION

Acids, bases, and salts. The three classes of compounds known respectively as acids, bases, and salts include the great majority of the compounds with which we shall have to deal. It is important, therefore, for us to consider each of these classes in a systematic way. The individual members belonging to each class will be discussed in detail in the appropriate places, but a few representatives of each class will be described in this chapter with special reference to the common properties in accordance with which they are classified.

The familiar acids. Hydrochloric acidis a gas composed of hydrogen and chlorine, and has the formula HCl. The substance is very soluble in water, and it is this solution which is usually called hydrochloric acid. Nitric acid is a liquid composed of hydrogen, nitrogen, and oxygen, having the formula HNO₃. As sold commercially it is mixed with about 32% of water. Sulphuric acid,

whose composition is represented by the formula H₂SO₄, is an oily liquid nearly twice as heavy as water, and is commonly called oil of vitriol.

Characteristics of acids. (1) All acids contain hydrogen. (2) When dissolved in water the molecules of the acid dissociate into two kinds of ions. One of these is always hydrogen and is the cation (+), while the other consists of the remainder of the molecule and is the anion (-). (3) The solution tastes sour. (4) It has the power to change the[Pg 107] color of certain substances called indicators. Thus blue litmus is changed to red, and yellow methyl orange is changed to red. Since all acids produce hydrogen cations, while the anions of each are different, the properties which all acids have in common when in solution, such as taste and action on indicators, must be attributed to the hydrogen ions.

DEFINITION: An acid is a substance which produces hydrogen ions when dissolved in water or other dissociating liquids.

Undissociated acids. When acids are perfectly free from water, or are dissolved in liquids like benzene which do not have the power of dissociating them into ions, they should have no real acid properties. This is found to be the case. Under these circumstances they do not affect the color of indicators or have any of the properties characteristic of acids.

The familiar bases. The bases most used in the laboratory are sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium hydroxide (Ca(OH)₂). These are white solids, soluble in water, the latter sparingly so. Some bases are very difficultly soluble in water. The very soluble ones with most pronounced basic properties are sometimes called the alkalis.

Characteristics of bases. 

(1) All bases contain hydrogen and oxygen. 

(2) When dissolved in water the molecules of the base dissociate into two kinds of ions. One of these is always composed of oxygen and hydrogen and is the anion. It has the formula OH and is called the hydroxyl ion. The remainder of the molecule, which usually consists of a single atom, is the cation. 

(3) The solution of a base has[Pg 108] a soapy feel and a brackish taste. 

(4) It reverses the color change produced in indicators by acids, turning red litmus blue, and red methyl orange yellow. Since all bases produce hydroxyl anions, while the cations of each are different, the properties which all bases have in common when in solution must be due to the hydroxyl ions.

DEFINITION: A base is a substance which produces hydroxyl ions when dissolved in water or other dissociating liquids.

Undissociated bases. Bases, in the absence of water or when dissolved in liquids which do not dissociate them, should have none of the properties characteristic of this class of substances. This has been found to be the case. For example, they have no effect upon indicators under these circumstances.

Neutralization. When an acid and a base are brought together in solution in proper proportion, the characteristic properties of each disappear. The solution tastes neither sour nor brackish; it has no effect upon indicators. There can therefore be neither hydrogen nor hydroxyl ions present in the solution. A study of reactions of this kind has shown that the hydrogen ions of the acid combine with the hydroxyl ions of the base to form molecules of water, water being a substance which is not appreciably dissociated into ions. This action of an acid on a base is called neutralization. The following equations express the neutralization of the three acids by three bases, water being formed in each case.

Na⁺, OH^- + H⁺, Cl^- = Na⁺, Cl^- + H₂O.

K⁺, OH^- + H⁺, NO₃^- = K⁺, NO₃^- + H₂O.

Ca⁺⁺, (OH)₂^— + H₂⁺⁺, SO₄^- = Ca⁺⁺, SO₄^— + 2H₂O. 

DEFINITION: Neutralization consists in the union of the hydrogen ion of an acid with the hydroxyl ion of a base to form water.

Salts. It will be noticed that in neutralization the anion of the acid and the cation of the base are not changed. If, however, the water is expelled by evaporation, these two ions slowly unite, and when the water becomes saturated with the substance so produced, it separates in the form of a solid called a salt.

DEFINITION: A salt is a substance formed by the union of the anion of an acid with the cation of a base.

Characteristics of salts. 

(1) From the definition of a salt it will be seen that there is no element or group of elements which characterize salts. 

(2) Salts as a class have no peculiar taste. 

(3) In the absence of all other substances they are without action on indicators.

(4) When dissolved in water they form two kinds of ions.

Heat of neutralization. If neutralization is due to the union of hydrogen ions with hydroxyl ions, and nothing more, it follows that when a given weight of water is formed in neutralization, the heat set free should always be the same, no matter from what acid and base the two kinds of ions have been supplied. Careful experiments have shown that this is the case, provided no other reactions take place at the same time. When 18g. of water are formed in neutralization, 13,700 cal. of heat are set free. This is represented in the equations

Na⁺, OH^- + H⁺, Cl^- = Na⁺, Cl^- + H₂O + 13,700 cal.

K⁺, OH^- + H⁺, NO₃^- = K⁺, NO₃^- + H₂O + 13,700 cal.

Ca⁺⁺, (OH)₂^- + H₂⁺⁺, SO₄^- = Ca⁺⁺, SO₄^- + 2H₂O + 2 × 13,700 cal. 

Neutralization a quantitative act. Since neutralization is a definite chemical act, each acid will require a perfectly definite weight of each base for its neutralization. For[Pg 110] example, a given weight of sulphuric acid will always require a definite weight of sodium hydroxide, in accordance with the equation

H₂, SO₄ + 2Na, OH = Na₂, SO₄ + 2H₂O. 

Determination of the ratio in neutralization. The quantities of acid and base required in neutralization may be determined in the following way. Dilute solutions of the two substances are prepared, the sulphuric acid being placed in one of the burettes (Fig. 34) and the sodium hydroxide in the other. The levels of the two liquids are then brought to the zero marks of the burettes by means of the stopcocks. A measured volume of the acid is drawn off into a beaker, a few drops of litmus solution added, and the sodium hydroxide is run in drop by drop until the red litmus just turns blue. The volume of the sodium hydroxide consumed is then noted. If the concentrations of the two solutions are known, it is easy to calculate what weight of sodium hydroxide is required to neutralize a given weight of sulphuric acid. By evaporating the neutralized solution to dryness, the weight of the sodium sulphate formed can be determined directly. Experiment shows that the weights are always in accordance with the equation in the preceding paragraph.

 

Extent of dissociation. The question will naturally arise, When an acid, base, or salt dissolves in water, do all the molecules dissociate into ions, or only a part of them? The experiments by which this question can be answered cannot be described here. It has been found, however, that only a fraction of the molecules dissociate. The percentage which will dissociate in a given case depends upon several conditions, the chief of which are: (1) The concentration of the solution. In concentrated solutions only a very small[Pg 111] percentage of dissociation occurs. As the solution is diluted the percentage increases, and in very dilute solutions it may be very large, though it is never complete in any ordinary solution. (2) The nature of the dissolved compound. At equal concentrations substances differ much among themselves in the percentage of dissociation. The great majority of salts are about equally dissociated. Acids and bases, on the contrary, show great differences. Some are freely dissociated, while others are dissociated to but a slight extent.

Strength of acids and bases. Since acid and basic properties are due to hydrogen and hydroxyl ions respectively, the acid or base which will produce the greatest percentage of these ions at a given concentration must be regarded as the strongest representative of its class. The acids and bases described in the foregoing paragraphs are all quite strong. In 10% solutions they are dissociated to about 50%, and this is also approximately the extent to which most salts are dissociated at this same concentration.

Partial neutralization. 1. Basic salts. The chemical action between an acid and a base is not always as complete as has been represented in the foregoing paragraphs. For example, if the base magnesium hydroxide (Mg(OH)₂) and hydrochloric acid (HCl) are brought together in the ratio of an equal number of molecules of each, there will be only half enough hydrogen ions for the hydroxyl ions present.

Mg, (OH)₂ + H, Cl = Mg, OH, Cl + H₂O.

Magnesium, hydroxyl, and chlorine ions are left at the close of the reaction, and under the proper conditions unite to form molecules of the compound Mg(OH)Cl. This compound, when dissolved, can form hydroxyl ions and therefore possesses basic properties; it can also form the ions of a salt (Mg and Cl), and has properties characteristic of salts. Substances of this kind are called basic salts.

DEFINITION: A basic salt is a substance which can give the ions both of a base and of a salt when dissolved in water. 

2. Acid salts. In a similar way, when sulphuric acid and sodium hydroxide are brought together in the ratio of equal numbers of the molecules of each, it is possible to have a reaction expressed by the equation

Na, OH + H₂, SO₄ = Na, H, SO₄ + H₂O.

The ions remaining after all the hydroxyl ions have been used up are those of an acid (H) and those of a salt (Na and SO₄). These unite to form the substance NaHSO₄, and as the solution becomes saturated with this substance through evaporation, it separates in the form of crystals. In solution this substance can give hydrogen ions, and therefore possesses acid properties; it can also give the ions characteristic of a salt. It is therefore called an acid salt.

DEFINITION: An acid salt is one which can give the ions of an acid and of a salt when in solution.

3. Normal salts. Salts which are the products of complete neutralization, such as Na₂SO₄, and which in solution can give neither hydrogen nor hydroxyl ions, but only the ions of a salt, are called normal salts to distinguish them from acid and basic salts.

Methods of expressing reactions between compounds in solution. Chemical equations representing reactions between substances in solution may represent the details of the reaction, or they may simply indicate the final products formed. In the latter case the formation of ions is not indicated. Thus, if we wish to call attention to the details of the reaction between sodium hydroxide and hydrochloric acid in solution, the equation is written as follows:

Na⁺, OH^- + H⁺, Cl^- = Na⁺, Cl^- + H₂O.

On the other hand, if we wish simply to represent the final products formed, the following is used.

NaOH + HCl = NaCl + H₂O.

Both of these methods will therefore be used:

Radicals. It has been emphasized that the hydroxyl group (OH) always [Pg 113]forms the anion of a base, while the group NO₃ forms the anion of nitric acid and sodium nitrate; the group SO₄, the anion of sulphuric acid and calcium sulphate. A group of elements which in this way constitutes a part of a molecule, acting as a unit in a chemical change, or forming ions in solution, is called a radical. Some of these radicals have been given special names, the names signifying the elements present in the radical. Thus we have the hydroxyl radical (OH) and the nitrate radical (NO₃).

DEFINITION: A radical is a group of elements forming part of a molecule, and acting as a unit in chemical reactions.

Names of acids, bases, and salts. Since acids, bases, and salts are so intimately related to each other, it is very advantageous to give names to the three classes in accordance with some fixed system. The system universally adopted is as follows:

Naming of bases. All bases are called hydroxides. They are distinguished from each other by prefixing the name of the element which is in combination with the hydroxyl group. Examples: sodium hydroxide (NaOH); calcium hydroxide (Ca(OH)₂); copper hydroxide (Cu(OH)₂).

Naming of acids. The method of naming acids depends upon whether the acid consists of two elements or three.

1. Binary acids. Acids containing only one element in addition to hydrogen are called binary acids. They are given names consisting of the prefix hydro-, the name of the second element present, and the termination -ic. Examples: hydrochloric acid (HCl); hydrosulphuric acid (H₂S).

2. Ternary acids. In addition to the two elements present in binary acids, the great majority of acids also contain oxygen. They therefore consist of three elements and[Pg 114] are called ternary acids. It usually happens that the same three elements can unite in different proportions to make several different acids. The most familiar one of these is given a name ending in the suffix -ic, while the one with less oxygen is given a similar name, but ending in the suffix -ous. Examples: nitric acid (HNO₃); nitrous acid (HNO₂). In cases where more than two acids are known, use is made of prefixes in addition to the two suffixes -icand -ous. Thus the prefix per- signifies an acid still richer in oxygen; the prefix hypo- signifies one with less oxygen.

Naming of salts. A salt derived from a binary acid is given a name consisting of the names of the two elements composing it, with the termination -ide. Example: sodium chloride (NaCl). All other binary compounds are named in the same way.

A salt of a ternary acid is named in accordance with the acid from which it is derived. A ternary acid with the termination -ic gives a salt with the name ending in -ate, while an acid with termination -ous gives a salt with the name ending in -ite. The following table will make the application of these principles clear:

ACIDS	SYMBOL	SALTS	SYMBOL
Hydrochloric	HCl	Sodium chloride	NaCl
Hypochlorous	HClO	Sodium hypochlorite	NaClO
Chlorous	HClO2	Sodium chlorite	NaClO2
Chloric	HClO3	Sodium chlorate	NaClO3
Perchloric	HClO4	Sodium perchlorate	NaClO4