Water vapor pressure over molten KH2PO4 and demonstration of water electrolysis at ∼300ºC

Rolf W. Berg, Aleksey Valerievich Nikiforov, Irina Petrushina, Niels J. Bjerrum

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A new potentially high-efficiency electrolyte for water electrolysis: molten monobasic potassium phosphate, KH2PO4 or KDP has been investigated at temperatures ∼275–325 °C. At these temperatures, KH2PO4 was found to dissociate into H2O gas in equilibrium with a melt mixture of KH2PO4—K2H2P2O7—KPO3—H2O. The water vapor pressure above the melt, when contained in a closed ampoule, was determined quantitatively vs. temperature by use of Raman spectroscopy with methane or hydrogen gas as an internal calibration standard, using newly established relative ratios of Raman scattering cross sections of water and methane or hydrogen to be 0.40 ± 0.02 or 1.2 ± 0.03. At equilibrium the vapor pressure was much lower than the vapor pressure above liquid water at the same temperature. Electrolysis was realized by passing current through closed ampoules (vacuum sealed quartz glass electrolysis cells with platinum electrodes and the electrolyte melt). The formation of mixtures of hydrogen and oxygen gases as well as the water vapor was detected by Raman spectroscopy. In this way it was demonstrated that water is present in the new electrolyte: molten KH2PO4 can be split by electrolysis via the reaction 2H2O → 2H2 + O2 at temperatures ∼275–325 °C. At these temperatures, before the start of the electrolysis, the KH2PO4 melt gives off H2O gas that pressurizes the cell according to the following dissociations: 2KH2PO4 ↔ K2H2P2O7 + H2O ↔ 2KPO3 + 2H2O. The spectra show however that the water by virtue of hydrogen-bonding has a high affinity for remaining in the melt. The formed hydrogen and oxygen gasses were detected by means of the characteristic Raman gas-phase spectra.
Original languageEnglish
JournalApplied Energy
Pages (from-to)269-275
Number of pages7
Publication statusPublished - 2016


  • Molten salt electrolyte
  • KDP
  • Elevated temperature water electrolysis
  • Vapor pressure
  • Phosphate-based electrolytes
  • Raman spectroscopy
  • Water electrolysis

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