How can I determine the boiling point of a compound using simple distillation?
Do you mean that the substance could be pure methanol, ethanol or 1-propanol? 

In that case there is a simple way to distinguish between the four options. A pure substance will have a T-V curve that consists of 2 straight lines, 1 running from $T=T_{start}$ to $T=T_{b}$ at $V=0$ and one running from $V=0$ to $V=V_{total}$ at $T=T_{b}$. Probably you will have some impurities which cause some small deviations from this perfect hook, but that will be the general shape. Determining the boiling temperature is just a matter of checking where the curve goes straight up. Depending on the temperature at which this happens you can identify methanol ($T_{b}\approx65$), ethanol ($T_{b}\approx78$) or 1-propanol ($T_{b}\approx97$).

The azeotropic mixture makes it a bit tricky, because the boiling points of 1-propanol and water are so close together, but the curve should show a distinct difference not going vertically up at a certain temperature.