An optimised thermostated electrochemical cell is designed and implemented. This is informed by experimental and computational studies characterizing the extent to which the thermostating of an electrochemical cell via a heated bath can be realised, both with the cell closed and open to the environment. The heat transfer in the system is simulated and probed experimentally; special emphasis is put on heat loss due to radiation and evaporation. Experiments and simulations demonstrate that these two mechanisms of heat transfer lead to a steady temperature in the cell that differs from that of the thermostat by ∼0.1 K. Simulations indicate that spatial inhomogeneities in the stationary temperature drive natural convective flows with a significant velocity. These new physical insights inform the optimization of a new electrochemical cell and its application in measurements of the impact frequency of silver nanoparticles as a function of temperature.