Manufacture of black powder was something that was worked out, by trial and error, over perhaps 200 years. It almost certainly started with the simple discovery that the mineral deposits found leaching out of dung hills and in old privy sites could make something burn very fast. Cloth or paper painted with a solution of it would , when dry, almost flash and disappear, charcoal would also burn quickly. Adding some sulfur ( known for also burning very hot) was then found to increase the speed of the reaction. Adjusting the ratios of the ingredients happened over years, as did learning to source the materials . There was no advanced chemical knowledge involved. So, sometime around mid-15th c. they had no idea that, when they discovered that an old cesspit from a wine tavern produced better saltpeter than one that had served beer , they were selecting a deposit higher in potassium nitrates than sodium nitrates, or that, when they boiled the solution with some wood ashes, they were precipitating out calcium nitrate. They just tinkered with things and gradually worked it out.

Nitrate explosives did take some development, but it was quite rapid, compared to black powder. From chemist Henri Braconnot's 1838 discovery that paper treated with nitric acid would become both a plastic ( considered the first plastic) and would burn rapidly, there were only a few years to chemist C.F. Schoenbein's 1845 discovery of a more effective technique for making what was soon called guncotton. Note these were chemists. Chemistry was growing as a science, and new discoveries were constant (if you tour the periodic table, you'll find a great number of elements identified in the for first 75 years of the 19th c. )

There was a also immediate recognition that this new explosive could replace black powder. But in practice it was far more tricky to get it to function as a propellant; the fast reaction meant the brisance ( the shattering power) was far too high to use safely. It took a great deal of experimentation before the French chemist Paul Vieille was able to work out a compound in 1884. The French revanchist General Boulanger immediately had arms developed that used it, and very quickly almost everyone but the United States did the same.

So, it was possible to invent black powder incrementally: saltpeter occurred naturally, and could already do tricks with paper and cloth, so tinkering with the recipe got them to gunpowder. Could someone from , say, 1400 have come up with smokeless powder by trial and error? It would have been difficult - very hard for them to decide to first try to make the concentrated nitric and sulfuric acids needed for the initial explosive, put them into non-reacting containers, vessels. And cooking it all incredibly carefully , in the age before thermometers, would have also been a challenge- a very dangerous challenge at that. To discover one of the additives that made shattering guncotton into smokeless powder ( for the English, it was camphor) seems also pretty hard...again, to get to that, there were 19th c. chemists experimenting, not medieval cooks tinkering. Then, finally, if the medieval tinkerers came up with smokeless powder there's the question of whether a medieval gun foundry could have made a cannon that could resist the much higher pressure.

If you'd like to be optimistic, though, Jules Verne had his American castaways make and use it , in his 1874 Mysterious Island. The stuff they made would have blown up their 1860 rifled muskets- and them with it- but the description is there, of how to make guncotton from what you might find on an island.

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Bert S Hall: Weapons and Warfare in Renaissance Europe

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