Temp of my mash when im stilling?!
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When you have a mixture of liquids, each with its own boiling point when pure, then the boiling point of the mix will lie somewhere in the middle, and this will depend on the relative concentrations of each liquid. Pure water boils at 100 deg C, and pure ethanol boils at 78.5 deg C, but a mixture of water and ethanol will boil at some point in between. The major point about distillation is that when a mixture like that boils, then the vapour given off is richer in the most volatile component, and when that vapour condenses then the resulting liquid has a lower boiling point than the mix it came from.
If you started with a mixture (fermented wash) that is mostly water & ethanol, with trace amounts of methanol, propanol, etc. then the net result will be that the most volatile components will tend to rise in greater quantity up the column than their less volatile cousins, and will be found in greatest concentration at the top. This would mean that methanol, the most volatile of the lot, will win the race and you will able to collect it and set it aside. This continues until you have collected all of the "heads" (components that are more volatile than ethanol), and you can then collect just ethanol with a trace of water. You cannot get rid of that small amount of water, as once you reach a mix of 96.5% ethanol/water, with a boiling point of 78.2 deg C (173 F), then you have reached a stable mix that no amount of re-boiling and re-condensation can change (at normal atmospheric pressure).