Phlogiston theory

The phlogiston theory, a superseded scientific theory, postulated the existence of a fire-like element dubbed phlogiston (/flɒˈdʒɪstən, floʊ-, -ɒn/) contained within combustible bodies and released during combustion. The name comes from the Ancient Greek φλογιστόν phlogistón (burning up), from φλόξ phlóx (flame). The idea of a phlogistic substance was first proposed in 1667 by Johann Joachim Becher and later put together more formally in 1697 by Georg Ernst Stahl. Phlogiston theory attempted to explain chemical processes such as combustion and rusting, now collectively known as oxidation. The theory was challenged by the concomitant mass increase and was abandoned before the end of the 18th century following experiments by Antoine Lavoisier in the 1770s and by other scientists. Phlogiston theory led to experiments that ultimately resulted in the identification (c. 1771), and naming (1777), of oxygen by Joseph Priestley and Antoine Lavoisier, respectively.

Phlogiston theory states that phlogisticated substances contain phlogiston and that they dephlogisticate when burned, releasing stored phlogiston, which is absorbed by the air. Growing plants then absorb this phlogiston, which is why air does not spontaneously combust and also why plant matter burns. This method of accounting for combustion was inverse to the oxygen theory by Antoine Lavoisier.

In general, substances that burned in the air were said to be rich in phlogiston; the fact that combustion soon ceased in an enclosed space was taken as clear-cut evidence that air had the capacity to absorb only a finite amount of phlogiston. When the air had become completely phlogisticated it would no longer serve to support the combustion of any material, nor would a metal heated in it yield a calx; nor could phlogisticated air support life. Breathing was thought to take phlogiston out of the body.

Joseph Black's Scottish student Daniel Rutherford discovered nitrogen in 1772, and the pair used the theory to explain his results. The residue of air left after burning, in fact, a mixture of nitrogen and carbon dioxide, was sometimes referred to as phlogisticated air, having taken up all of the phlogiston. Conversely, when Joseph Priestley discovered oxygen, he believed it to be dephlogisticated air, capable of combining with more phlogiston and thus supporting combustion for longer than ordinary air.

Empedocles had formulated the classical theory that there were four elements—water, earth, fire, and air—and Aristotle reinforced this idea by characterising them as moist, dry, hot, and cold. Fire was thus thought of as a substance, and burning was seen as a process of decomposition that applied only to compounds. Experience had shown that burning was not always accompanied by a loss of material, and a better theory was needed to account for this.

In 1667, Johann Joachim Becher published his book Physica subterranea, which contained the first instance of what would become the phlogiston theory. In his book, Becher eliminated fire and air from the classical element model and replaced them with three forms of the earth: terra lapidea, terra fluida, and terra pinguis. Terra pinguis was the element that imparted oily, sulfurous, or combustible properties. Becher believed that terra pinguis was a key feature of combustion and was released when combustible substances were burned. Becher did not have much to do with phlogiston theory as it is known now, but he had a large influence on his student Stahl. Becher's main contribution was the start of the theory itself, however much of it was changed after him. Becher's idea was that combustible substances contain an ignitable matter, the terra pinguis.

In 1703, Georg Ernst Stahl, a professor of medicine and chemistry at Halle, proposed a variant of the theory in which he renamed Becher's terra pinguis to phlogiston, and it was in this form that the theory probably had its greatest influence. The term 'phlogiston' itself was not something that Stahl invented. There is evidence that the word was used as early as 1606, and in a way that was very similar to what Stahl was using it for. The term was derived from a Greek word meaning inflame. The following paragraph describes Stahl's view of phlogiston:

To Stahl, metals were compounds containing phlogiston in combination with metallic oxides (calces); when ignited, the phlogiston was freed from the metal leaving the oxide behind. When the oxide was heated with a substance rich in phlogiston, such as charcoal, the calx again took up phlogiston and regenerated the metal. Phlogiston was a definite substance, the same in all its combinations.