(We think.) The first recorded example of military flamethrowing appears in Greek historian Thucydides’ account of the Peloponnesian War between Athens ad Sparta in 431 to 404 BCE.
During the Battle of Delium in 424 BCE, the Athenians were surrounded and dug in at a fort made of wood and vines. Rather than wait them out, the Spartans hollowed out a great wooden log, lined it with an iron pipe, filled it with a smoldering mixture of coal, sulfur, and pitch. They attached a giant bellows to the Spartan end of the pipe, and were able to blow and burn down the Athenians’ fort.
After this, it appears the Spartan invention became a standard weapon in war.
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