Phlogiston – Early Science at Work

One of the earlier scientific concepts was phlogiston, and it is of interest to follow why this concept went wrong, if it did. One of the major problems for early theory was that nobody knew very much. Materials had properties, and these were referred to as principles, which tended to be viewed either as abstractions, or as physical but weightless entities. We would not have such difficulties, would we? Um, spacetime?? Anyway, they then observed that metals did something when heated in air:

M   + air +  heat        ÞM(calx) ±  ???  (A calx was what we call an oxide.)

They deduced there had to be a metallic principle that gives the metallic properties, such as ductility, lustre, malleability, etc., but they then noticed that gold refuses to make a calx, which suggested there was something else besides the metallic principle in metals. They also found that the calx was not a mixture, thus rust did not lead to iron being attached to a lodestone. This may seem obvious to us now, but conceptually this was significant. For example, if you mix blue and yellow paint, you get green and they cannot readily be unmixed, nevertheless it is a mixture. Chemical compounds are not mixtures, even though you might make them by mixing two materials. Even more important was the work by Paracelsus, the significance of which is generally overlooked. He noted there were a variety of metals, calces and salts, and he generalized that acid plus metal or acid plus metal calx gave salts, and each salt was specifically different, and depended only on the acid and metal used. He also recognized that what we call chemical compounds were individual entities, that could be, and should be, purified.

It was then that Georg Ernst Stahl introduced into chemistry the concept of phlogiston. It was well established that certain calces reacted with charcoal to produce metals (but some did not) and the calx was usually heavier than the metal. The theory was, the metal took something from the air, which made the calx heavier. This is where things became slightly misleading because burning zinc gave a calx that was lighter than the metal. For consistency, they asserted it should have gained but as evidence poured in that it had not, they put that evidence in a drawer and did not refer to it. Their belief that it should have was correct, and indeed it did, but this avoiding the “data you don’t like” leads to many problems, not the least of which include “inventing” reasons why observations do not fit the theory without taking the trouble to abandon the theory. This time they were right, but that only encourages the act. As to why there was the problem, zinc oxide is relatively volatile and would fume off, so they lost some of the material. Problems with experimental technique and equipment really led to a lot of difficulties, but who amongst us would do better, given what they had?

Stahl knew that various things combusted, so he proposed that flammable substances must contain a common principle, which he called phlogiston. Stahl then argued that metals forming calces was in principle the same as materials like carbon burning, which is correct. He then proposed that phlogiston was usually bound or trapped within solids such as metals and carbon, but in certain cases, could be removed. If so, it was taken up by a suitable air, but because the phlogiston wanted to get back to where it came from, it got as close as it could and took the air with it. It was the phlogiston trying to get back from where it came that held the new compound together. This offered a logical explanation for why the compound actually existed, and was a genuine strength of this theory. He then went wrong by arguing the more phlogiston, the more flammable the body, which is odd, because if he said some but not all such materials could release phlogiston, he might have thought that some might release it more easily than others. He also argued that carbon was particularly rich in phlogiston, which was why carbon turned calces into metals with heat. He also realized that respiration was essentially the same process, and fire or breathing releases phlogiston, to make phlogisticated air, and he also realized that plants absorbed such phlogiston, to make dephlogisticated air.

For those that know, this is all reasonable, but happens to be a strange mix of good and bad conclusions. The big problem for Stahl was he did not know that “air” was a mixture of gases. A lesson here is that very seldom does anyone single-handedly get everything right, and when they do, it is usually because everything covered can be reduced to a very few relationships for which numerical values can be attached, and at least some of these are known in advance. Stahl’s theory was interesting because it got chemistry going in a systemic way, but because we don’t believe in phlogiston, Stahl is essentially forgotten.

People have blind spots. Priestley also carried out Lavoisier’s experiment:  2HgO  + heat   ⇌   2Hg  + O2and found that mercury was lighter than the calx, so argued phlogiston was lighter than air. He knew there was a gas there, but the fact it must also have weight eluded him. Lavoisier’s explanation was that hot mercuric oxide decomposed to form metal and oxygen. This is clearly a simpler explanation. One of the most important points made by Lavoisier was that in combustion, the weight increase of the products exactly matched the loss of weight by the air, although there is some cause to wonder about the accuracy of his equipment to get “exactly”. Measuring the weight of a gas with a balance is not that easy. However, Lavoisier established the fact that matter is conserved, and that in chemical reactions, various species react according to equivalent weights. Actually, the conservation of mass was discovered much earlier by Mikhail Lomonosov, but because he was in Russia, nobody took any notice. The second assertion caused a lot of trouble because it is not true without a major correction to allow for valence. Lavoisier also disposed of the weightless substance phlogiston simply by ignoring the problem of what held compounds together. In some ways, particularly in the use of the analytical balance, Lavoisier advanced chemistry, but in disposing of phlogiston he significantly retarded chemistry.

So, looking back, did phlogiston have merit as a concept? Most certainly! The metal gives off a weightless substance that sticks to a particular gas can be replaced with the metal gives off an electron to form a cation, and the oxygen accepts the electron to form an anion. Opposite charges attract and try to bind together. This is, for the time, a fair description of the ionic bond. As for weightless, nobody at the time could determine the weight difference between a metal and a metal less one electron, if they could work out how to make it. Of course the next step is to say that the phlogiston is a discrete particle, and now valence falls into place and modern chemistry is around the corner. Part of the problem there was that nobody believed in atoms. Again, Lomonosov apparently did, but as I noted above, nobody took any notice of him. Of course, is it is far easier to see these things in retrospect. My guess is very few modern scientists, if stripped of their modern knowledge and put back in time would do any better. If you think you could, recall that Isaac Newton spent a lot of time trying to unravel chemistry and got nowhere. There are very few ever that are comparable to Newton.