Phlogiston theory

The alchemist and physician J. J. Becher proposed the phlogiston theory

The phlogiston theory is a superseded scientific theory that postulated that a fire-like element called phlogiston is contained within combustible bodies and released during combustion. The name comes from the Ancient Greek φλογιστόν phlogistón (burning up), from φλόξ phlóx (flame). It was first stated in 1667 by Johann Joachim Becher, and then put together more formally by Georg Ernst Stahl. The theory attempted to explain burning processes such as combustion and rusting, which are now collectively known as oxidation.

Theory

Phlogisticated substances are substances that contain phlogiston and dephlogisticate when burned. Dephlogisticating is when the substance simply releases the phlogiston inside of it and that phlogiston 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 as well as it does.

In the following quote, Becher described phlogiston as a process that explained combustion through a process that was opposite to that of oxygen.

In general, substances that burned in 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 air had become completely phlogisticated it would no longer serve to support 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.^[1]

Joseph Black's 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 oxygen was first discovered, it was thought to be dephlogisticated air, capable of combining with more phlogiston and thus supporting combustion for longer than ordinary air.^[2]

History of the theory

Johann Joachim Becher

In 1667, Johann Joachim Becher published his book Physica subterranea, which was the first mention of what would become the phlogiston theory. Traditionally, alchemists considered that there were four classical elements: fire, water, air, and earth. In his book, Becher eliminated fire, water, and air from the classical element model and replaced them with three forms of earth: terra lapidea, terra fluida, and terra pinguis.^[3][4] Terra pinguis was the element that imparted oily, sulphurous, or combustible properties.^[5] Becher believed that terra pinguis was a key feature of combustion and was released when combustible substances were burned.^[3] Becher did not have much to do with phlogiston theory as we know it now, but he had a large influence on his student Stahl. Becher's main contribution was the start of the theory itself, however much it was changed after him.^[6] Becher's idea was that combustible substances contain an ignitable matter, the terra pinguis. ^[7]

Georg Ernst Stahl

Georg Ernst Stahl

In 1703 Georg Ernst Stahl, 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.^[8] 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.^[6] The term was derived from a Greek word meaning to inflame. The following paragraph describes Stahl's view of phlogiston well:

To Stahl, metals were compounds containing phlogiston in combination with metallic oxides (calces); on ignition 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. ^[7]

Stahl's first definition of phlogiston first appeared in his "Zymotechnia fundamentalis", published in 1697. His most quoted definition was found in the treatise on chemistry entitled "Fundamenta chymiae" in 1723.^[9] According to Stahl, phlogiston was a substance that was not able to be put into a bottle, but could be transferred nonetheless. To him, wood was just a combination of ash and phlogiston, and making a metal was as simple as getting a metal calx and adding phlogiston. ^[7]

J. H. Pott

J. H. Pott, a student of one of Stahl's students, expanded the theory and attempted to make it much more understandable to people. He compared phlogiston to light or fire, it being a substance that everyone knows what it is but can not give an entirely satisfactory definition. He thought that phlogiston should not be considered as a particle but as an essence that permeates substances. He argues that in a pound of any substance one could not simply pick out the particles of phlogiston.^[6] Pott also starts to worry about the fact that sometimes when certain substances are burned they gain either weight or size, when if they are losing phlogiston they should be losing one of the two. According to Pott, phlogiston is the basic fire principle and can not be obtained by itself. When flames are seen, it is phlogiston mixed with water. When mixed with earthy matter, it can not burn very well. Phlogiston is in everything in the universe and when it meets acid it reacts and is released as heat. His properties are as follows:

1. The form of phlogiston consists of a circular movement around its axis.
2. When homogeneous it can not be consumed or dissipated in fire.
3. The reason it causes expansion in most bodies is unknown, but not accidental. It is proportional to the compactness of the texture of the bodies or to the intimacy of their constitution.
4. The increase of weight during calcination is evident only after a long time, and is due either to the fact that the particles of the body become more compact, decrease the volume and hence increase the density as in the case of lead; ir that little heacy particles of air become lodged in the substance as in the case of powdered zinc oxide.
5. Air attracts the phlogiston of bodies.
6. When set in motion, phlogiston is the chief active principle in nature of all inanimate bodies.
7. It is the basis of colors.
8. It is the principle agent in fermentation.^[6]

Pott did not change much about the theory, he just fleshed out the details and made them more understandable to most people.

Others

Johann Juncker also created a very complete picture of phlogiston. When reading Stahl's work, he assumed that phlogiston was in fact very material. He therefore come to the conclusion that phlogiston has the property of levity, or that it makes the compound that it is in much lighter than it would be without the phlogiston. He also showed that air was needed for combustion by putting substances in a sealed flask and trying to burn them. ^[6]

Guillaume-Francois Rouelle brought the theory of phlogiston to France, and he was a very influential scientist and teacher so it gained quite a strong foothold very quickly. Many of his students became very influential scientist in their own right, Lavoisier included.^[7] The French viewed phlogiston as a very subtle principle that vanishes in all analysis, yet it is in all bodies. Essentially they followed straight from Stahl's theory. ^[6]

Challenge and demise

Eventually, quantitative experiments revealed problems, including the fact that some metals gained mass when they burned, even though they were supposed to have lost phlogiston. Some phlogiston proponents explained this by concluding that phlogiston had negative mass; others, such as Louis-Bernard Guyton de Morveau, gave the more conventional argument that it was lighter than air. However, a more detailed analysis based on Archimedes' principle, the densities of magnesium and its combustion product showed that just being lighter than air could not account for the increase in mass. Stahl himself did not address the problem of the metals that burn gaining weight, but those who followed his ideas and did not question his ideas were the ones that worked on this problem.^[9]

During the eighteenth century, as it became clear that metals gained mass when they were oxidized, phlogiston was increasingly regarded as a principle rather than a material substance.^[10] By the end of the eighteenth century, for the few chemists who still used the term phlogiston, the concept was linked to hydrogen. Joseph Priestley, for example, in referring to the reaction of steam on iron, whilst fully acknowledging that the iron gains mass as it binds with oxygen to form a calx, iron oxide, iron also loses “the basis of inflammable air (hydrogen), and this is the substance or principle, to which we give the name phlogiston.”^[11] Following Lavoisier’s description of oxygen as the oxidizing principle (hence its name, from Ancient Greek: oksús, “sharp”; génos, “birth”, referring to oxygen's role in the formation of acids), Priestley described phlogiston as the alkaline principle.^[12]

Phlogiston remained the dominant theory until the 1780s when Antoine-Laurent Lavoisier showed that combustion requires a gas that has mass (oxygen) and could be measured by means of weighing closed vessels.^[13] The use of closed vessels also negated the buoyancy that had disguised the mass of the gases of combustion. These observations solved the mass paradox and set the stage for the new oxygen theory of combustion. Experienced chemists who supported Stahl's phlogiston theory attempted to respond to the challenges suggested by Lavoisier and the newer chemists. In doing so, phlogiston theory became more complicated and assumed too much, contributing to the overall demise of the theory.^[14]

Many people tried to remodel their theories on phlogiston in order to have the theory work with what Lavoisier was doing in his experiments. Pierre Macquer reworded his theory many times, and even though he is said to have thought the theory of phlogiston was doomed, he stood by phlogiston and tried to make it work.^[15]

Notes

1. James Bryan Conant, ed. The Overthrow of Phlogiston Theory: The Chemical Revolution of 1775–1789. Cambridge: Harvard University Press (1950), 14. OCLC 301515203.
2. "Priestley, Joseph". Spaceship-earth.de. Retrieved 2009-06-05.
3. Bowler, Peter J (2005). Making modern science: A historical survey. Chicago: University of Chicago Press. p. 60.
4. Becher, Physica Subterranea p. 256 et seq.
5. Brock, William Hodson (1993). The Norton history of chemistry (1st American ed.). New York: W. W. Norton. ISBN 0-393-03536-0.
6. White, John Henry (1973). The History of Phlogiston Theory. Ney York, N.Y.: AMS Press Inc. ISBN 0404069304.
7. Leicester, Henry M.; Klickstein, Herbert S. (1965). A Source Book in Chemistry. Cambridge, Massachusetts: Harvard University Press.
8. Mason, Stephen F., (1962). A History of the Sciences (revised edition). New York: Collier Books. Ch. 26.
9. White, John Henry (1973). The History of Phlogiston Theory. Ney York, N.Y.: AMS Press Inc. ISBN 0404069304.
10. For a discussion of how the term phlogiston was understood during the eighteenth century, see: James R Partington & Douglas McKie; "Historical studies on the phlogiston theory"; Annals of Science, 1937, 2, 361–404; 1938, 3, 1–58; and 337–71; 1939, 5, 113–49. Reprinted 1981 as ISBN 978-0-405-13895-9.
11. Joseph Priestley; Considerations on the doctrine of phlogiston, and the decomposition of water; Philadelphia, Thomas Dobson, 1796; p.26.
12. Joseph Priestley; Heads of lectures on a course of experimental philosophy; London, Joseph Johnson, 1794.
13. Nicholas W. Best, "Lavoisier's 'Reflections on Phlogiston' I: Against Phlogiston Theory", Foundations of Chemistry, 2015, 17, 137-151.
14. Ihde, Aaron (1964). The Development of Modern Chemistry. New York: Harper & Row. p. 81.
15. Partington, J.R.; McKie, Douglas (1981). Historical Studies on the Phlogiston Theory. Arno Press. ISBN 0405138504.