Sciencemadness Discussion Board

Fractional distillation at high altitude, predicting Azeotropic BP

Endo - 22-4-2019 at 12:10

Having done some fractional distillations here at 7300 ft I am trying to wrap my head around the decreased temperatures and how it affects a two component mixture, ethanol/water and 1,4 Dioxane/ water when trying to get a good azeotropic fraction. I have been just doing my distillations blind and capturing the fractions where temps hit a plateau. I figured it would be nice to be able to try to find a calculation that I could use to correct my target temperature by looking up the barometric pressure on NOAA and converting it from in Hg.

I did some digging and found a couple pages and read through them trying to get my head around how a change in the overall pressure would affect the azeotropic boiling point of the mixture.

Raoult's Law and ideal mixtures
And
Ideal fractional distillation

Vapor Pressure


Unfortunately in thinking through the details I am despairing of finding an easy conversion. Anybody out there have a simple process or know of a correction table that works with mixtures of liquids?

Thanks!!


happyfooddance - 22-4-2019 at 13:49

The problem is that there is no easy conversion, because the underlying mechanics of even a binary azeotrope is so so so complex, and you are trying to define it with two parameters (vapor pressure and temp.)

Not all azeotropes are even formed by the same dominant mechanics. It's best to look at the particular azeotrope to learn more about its characteristics. For example, many azeotropes of water can be broken or shift as the boiling point of the mixture gets close to the freezing point of water. This can be safely assumed to be because of the properties of water in the liquid phase at colder temps.

As for distilling @7200', that is a drop to about 23in Hg or about 580 torr, so will only change the boiling point a few degrees. Use a nomograph for a crude (yet sometimes very effective) way of determining your unknowns from your knowns:
https://erowid.org/archive/rhodium/chemistry/equipment/pictu...

The ethanol water azeotrope disappears at around 17°C, so you will need a better vacuum source.