Binodal curves of PEG (400, 4000 and 6000) + Na2SO4 ATPS were determined.
Tie-lines were experimentally determined for aqueous (PEG 400 + Na2SO4) system.
Influence of caffeine on LLE of aqueous (PEG 400 + Na2SO4) system was investigated.
Partitioning of caffeine in aqueous (PEG 400 + Na2SO4) system was investigated.
Caffeine partition showed to be dependent on temperature and TLL.