Energy crisis is a prognosis predicted in many cases with the indiscriminate encroachment of conventional energy sources for applications on a massive scale. This prediction, further emboldened by the marked surge in global average temperatures, attributed to climate change and global warming, the necessity to conserve the environment and explore alternate sources of energy is at an all-time high. Despite being among the lead candidates for such sources, solar energy is utilized far from its vast potential possibilities due to predominant economic constraints. Even while there is a growing need for solar panels at more affordable rates, the other options to harness better out of sun's energy is to optimize and improvise existing technology. One such technology is the heat pipe used in Evacuated Tube Collectors (ETC). The applications of heat pipe have been gaining momentum in various fields since its inception and substantial volumes of research have explored optimizing and improving the technology which is proving effective in heat recovery and heat transfer better than conventional systems. This paper carries out a computational analysis on a comparative simulation between two working fluids within heat pipe of same geometry. It further endeavors to study the multiphase transitions within the heat pipe. The work is carried out using ANSYS Fluent with inputs taken from solar data for the location of Vellore, Tamil Nadu. A wickless, gravity-assisted heat pipe (GAHP) is taken for the simulation. Water and ammonia are used as the working fluids for comparative multiphase analysis to arrive at the difference in heat transfer at the condenser section. It is demonstrated that a heat pipe ETC with ammonia as working fluid showed higher heat exchange (temperature difference) as against that of water as working fluid. The multiphase model taken aided in study of phase transitions within both cases and supported the result of ammonia as fluid being a better candidate. © 2017 Published under licence by IOP Publishing Ltd.