Hydrogen is evolved from water by many metals, which are capable of forming oxides in air—that is, which are capable of burning or combining with oxygen. The capacity of metals for combining with oxygen, and therefore for decomposing water, or for the evolution of hydrogen, is very dissimilar.9 Among metals, potassium and sodium exhibit considerable energy in this respect. The first occurs in potash, the second in soda. They are both lighter than water, soft, and easily change in air. By bringing one or the other of them in contact with water at the ordinary temperature,10 a quantity of hydrogen, corresponding with the amount of the metal taken, may be directly obtained. One gram of hydrogen, occupying a volume of 11·16 litres at 0° and 760 mm., is evolved from every 39 grams of potassium, or 23 grams of sodium. The phenomenon may be observed in the following way: a solution of sodium in mercury—or ‘sodium amalgam,’ as it is generally called—is poured into a vessel containing water, and owing to its weight sinks to the bottom; the sodium held in the mercury then acts on the water like pure sodium, liberating hydrogen. The mercury does not act here, and the same amount of it as was taken for dissolving the sodium is obtained in the residue. The hydrogen is evolved gradually in the form of bubbles, which pass through the liquid.
Beyond the hydrogen evolved and a solid substance, which remains in solution (it may be obtained by evaporating the resultant solution) no other products are here obtained. Consequently, from the two substances (water and sodium) taken, the same number of new substances (hydrogen and the substance dissolved in water) have been obtained, from which we may conclude that the reaction which here takes place is a reaction of double decomposition or of substitution. The resultant solid is nothing else but the so-called caustic soda (sodium hydroxide), which is made up of sodium, oxygen, and half of the hydrogen contained in the water. Therefore, the substitution took place between the hydrogen and the sodium, namely half of the hydrogen in the water was replaced by the sodium, and was evolved in a free state. Hence the reaction which takes place here may be expressed by the equation H2O + Na = NaHO + H; the meaning of this is clear from what has already been said.11
Sodium and potassium act on water at the ordinary temperature. Other heavier metals only act on it with a rise of temperature, and then not so rapidly or vigorously. Thus magnesium and calcium only liberate hydrogen from water at its boiling point, and zinc and iron only a red heat, whilst a whole series of heavy metals, such as copper, lead, mercury, silver, gold, and platinum, do not in the least decompose water at any temperature, and do not replace its hydrogen.
From this it is clear that hydrogen may be obtained by the decomposition of steam by the action of iron (or zinc) with a rise of temperature. The experiment is conducted in the following manner: pieces of iron (filings, nails, &c.), are placed in a porcelain tube, which is then subjected to a strong heat and steam passed through it. The steam, coming into contact with the iron, gives up its oxygen to it, and thus the hydrogen is set free and passes out at the other end of the tube together with undecomposed steam. This method, which is historically very significant,12 is practically inconvenient, as it requires a rather high temperature. Further, this reaction, as a reversible one (a red-hot mass of iron decomposes a current of steam, forming oxide and hydrogen; and a mass of oxide of iron, heated to redness in a stream of hydrogen, forms iron and steam), does not proceed in virtue of the comparatively small difference between the affinity of oxygen for iron (or zinc) and for hydrogen, but only because the hydrogen escapes, as it is formed, in virtue of its elasticity.13 If the oxygen compounds—that is, the oxides—which are obtained from the iron or zinc, be able to pass into solution, then the affinity acting in solution is added, and the reaction may become non-reversible, and proceed with comparatively much greater facility.14 As the oxides of iron and zinc, by themselves insoluble in water, are capable of combining with (have an affinity for) acid oxides (as we shall afterwards fully consider),