That’s right. Note however that the solvent interacts as well, not just the solutes.
Careful also about which temperature you seek knowledge about, the pot liquid temperature or the condensing vapor temperature, they will be different. The mass transfer and heat transfer characteristics of the device will impact all of this, in addition to the vapor liquid equilibria. Many people assume “equilibrium” for distillation, but in most cases it is really “rate based” which is driven by mass transfer phenomena. There is a chance there is pressure drop from the heating flask to the cold trap. Anyone tracking this during their runs? The pressure has an affect on VLE too.
There are well established methods for determining VLE for multicomponent mixtures. Taking a mixture of terpenes and doing those experiments might be helpful, but maybe not. Can share some articles when I did them out. I’ve seen research labs charge up to $100k for a single study.