> That is to say, the first ounces distilled should have a higher concentration of methanol. The liquid in the mash is a mixture of 4 or more different liquids

> That is to say, the first ounces distilled should have a higher concentration of methanol. The liquid in the mash is a mixture of 4 or more different liquids, in wildly different proportions. Most of the mixture is not even methanol, but water. This mixture has a single boiling point, which is determined by the chemistry of the constituents. (For example, the boiling point of a mixture that contains a little bit of water and a lot of ethanol is _lower_ than the boiling point of pure ethanol. You see why trying to make predictions based purely on the boiling point of methanol won't work, do you? You can estimate vapor composition using variants of Raoult's law [1] but only after accounting carefully for azeotropy.) Simple distillation does a poor job of separating even water from alcohol: at the end of your first distillation you'll consider yourself lucky if you got an alcohol percentage over 35%. It will also have some ethyl acetate and (if you used drupe mash) ethyl carbamate. The latter has a boiling point of 185C, so could not end up there at all under a naive/folk model of distillation. The foreshot has plenty of its own components, including ketones like acetone (which has a lower boiling point than methanol), water of course, alcohols, occasionally copper from the equipment, but it will certainly not be pure methanol, and while methanol concentration will be somewhat higher, the vast majority of the methanol won't come from the first ounces. It will also be warm, and taste awful: taking a sip will teach you a lesson, but not give you methanol poisoning. Chemistry is complicated, but based on our current understanding getting accidental methanol poisoning from unadulterated home distilled alcohol would be nothing short of a chemical miracle. You might be able to pull it off deliberately if you try hard, but you'll need good skills and good equipment so that you can isolate it (it's significantly less potent if taken with ethanol, due to metabplic effects). That's not to say you won't get alcohol poisoning, of course: ethanol is an alcohol, and it is poisonous. [1] https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Equilibria/Physical_Equilibria/Raoults_Law_and_Ideal_Mixtures_of_Liquids https://chem.libretexts.org/Bookshelves/Physical_and_Theoret...