Their mouths aren’t big enough, but they do have extremely strong mandibles, essentially little arms on their faces that can be used to carry things or hold food. In terms of why they hurt, first of all, ant mandibles are extremely strong for their size, ants are famous for their strength. In terms of why they hurt, it comes down to basic evolution. When an ant wants to defend itself it bites, if the bitee wasn’t aware of the bite it wouldn’t be an effective defense mechanism and those ants got killed/eaten. The ants that successfully warded off the threat survived and passed down the painful bite mechanism to their offspring.
In terms of how the bite hurts, the mandibles are designed to inflict the strongest signal for their size, rather super tiny punctures they will slice and tear the flesh to create the most pain possible, even if the damage to the tissue is insignificant. Some ant species also have venom that can chemically trigger pain signals outside of tissue damange.
Most ants aren’t large enough that their jaws (called mandibles) could penetrate the outer dead layer of skin, and thus cause pain.
However the majority of ant species are armed with venom to one degree or another. Many, but not all of those have an egg-laying structure called an ovipositor, that is modified into a stinger. These can be quite long with respect to the size of their abdomen. So pain your referring to is probably a result of venom produced prom their stings, and not their bites.
Ants produce a wide variety of compounds in their venoms and this is a subject of a great deal of scientific research.
For example, Wood Ants in the genus *Formica* produce large amounts of Formic acid, named after this genus. These are somewhat large as far as ants go. Instead of stingers these ants are strong enough to spray tiny streams of this acid, potentially blinding or burning the lungs of animals that attack the nest.
They have extremely powerful mandibles, that can pinch and break skin. A lot of ants have what is essentially incorporated latches connecting their muscles, allowing them to store a much higher amount of potential energy, than what the muscles could handle alone. Like *Odontomachus bauri* a species of trap jaw ant, can close their mandibles at up to 230km/h, with an order of force 300x the ant’s weight, it’s so powerful that they can catapult themselves away from predators.
As well as just being able to bite you many ants have bonus weapons. Some have stingers on their thorax to inject venom, like bull ants, fire ants and bullet ants, bullet ants being notably excruciatingly painful. Other ants, like wood ants, create formic acid in their thorax which they can use to spray potential threats as a massive group. The formic acid isn’t too bad for mammals, as it’s primary use tends to be to dissolve the inside of other athropods, after breaking open their exoskeleton with bites, during hunting efforts. But none the less would make your eyes and sinuses pretty uncomfortable, and would burn any open wounds or bites.
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