I have used vinegar as weedkiller. It does kill plants, especially grass and green leafy types. You need to use the distilled (clear) stuff, but doing a bit of Googling I found that you need 10% acetic acid concentration to stand any chance of killing the roots, but the stuff available in shops is only 5%. There is information available on the internet, as I recall, many people recommend mixing it with salt and washing up liquid, because not much survives salt and the washing up liquid helps the fluid stick to the leaves.
I also made some of my own weedkiller by mixing about 2kg of salt into a large bucket of boiling water, stirring to dissolve the salt and then adding a bottle of cheap bleach. It worked quire well, but the weeds eventually grew back. have recently used one of those pressure cannisters of Round Up, which can be refilled, so when the Round Up is gone I am going to try using the cannister to spray my own concoction.