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Critical assessment of water enthalpy characterization through dark environment evaporation

Comparative evaporation rate testing in the absence of solar irradiation is a widely adopted method for establishing and characterizing a reduced vaporization enthalpy of water within an interfacial solar evaporator. However, the assumption of equal energy input between cases is not generally valid, and renders this characterization method misleading. Larger evaporation rates result from interfacial evaporators in dark conditions, mostly due to expanded surface areas. This causes greater evaporation rates, more evaporative cooling, and larger temperature differentials with the environment. We provide theoretical and experimental evidence to prove that these temperature differences cause large differences in environmental energy input, such that equal energy input cannot be assumed. Evaluation of our data within a transient analytical model enables quantification of the energy input differences and calculation of the vaporization enthalpy. This shows that differences in evaporation rate correspond to differences in energy input, and that vaporization enthalpy is not reduced below the theoretical value. The magnitude of increased energy input also agrees well with the increase of dark environment evaporation rates typically reported for interfacial evaporators, providing an alternative explanation for previous literature results. Further, we exemplify that the results of this characterization method contradict differential scanning calorimetry results, which are often used to make conclusions about vaporization enthalpy reduction and water state modification within evaporator materials. Thus, we conclude that this method should not be used to make conclusions about vaporization enthalpy reductions within interfacial evaporator materials. These results emphasize that the current understanding of vaporization enthalpy reduction within evaporator materials requires re-evaluation.