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The use of chemical weapons is prohibited under customary international humanitarian law.Chemical warfare is different from the use of conventional weapons or nuclear weapons because the destructive effects of chemical weapons are not primarily due to any explosive force.

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Kautilya's "Arthashastra", a statecraft manual of the same era, contains hundreds of recipes for creating poison weapons, toxic smokes, and other chemical weapons. In the second century BC, writings of the Mohist sect in China describe the use of bellows to pump smoke from burning balls of toxic plants and vegetables into tunnels being dug by a besieging army.The offensive use of living organisms (such as anthrax) is considered biological warfare rather than chemical warfare; however, the use of nonliving toxic products produced by living organisms (e.g.toxins such as botulinum toxin, ricin, and saxitoxin) is considered chemical warfare under the provisions of the Chemical Weapons Convention (CWC).Sparta was not alone in its use of unconventional tactics in ancient Greece; Solon of Athens is said to have used hellebore roots to poison the water in an aqueduct leading from the River Pleistos around 590 BC during the siege of Kirrha.The earliest archaeological evidence of gas warfare is during the Roman–Persian wars.Under this Convention, any toxic chemical, regardless of its origin, is considered a chemical weapon unless it is used for purposes that are not prohibited (an important legal definition known as the General Purpose Criterion).

About 70 different chemicals have been used or stockpiled as chemical warfare agents during the 20th century.

In the 17th century during sieges, armies attempted to start fires by launching incendiary shells filled with sulfur, tallow, rosin, turpentine, saltpeter, and/or antimony.

Even when fires were not started, the resulting smoke and fumes provided a considerable distraction.

The earliest recorded use of gas warfare in the West dates back to the fifth century BC, during the Peloponnesian War between Athens and Sparta.

Spartan forces besieging an Athenian city placed a lighted mixture of wood, pitch, and sulfur under the walls hoping that the noxious smoke would incapacitate the Athenians, so that they would not be able to resist the assault that followed.

Homer's epics, the Iliad and the Odyssey, allude to poisoned arrows used by both sides in the legendary Trojan War (Bronze Age Greece).