The　results　of　the　coordination　form　of　low-concentration　ions　in　molten　salt　have　great　reference　significance　for　exploring　the　electrolysis　reaction　mechanism.　Given　the　low　concentration　of　tungsten　ions　after　the　electrochemical　dissolution　of　tungsten　carbide,　this　can　be　difficult　to　judge　the　coordination　form　of　tungsten　ions　through　spectral　characterization.　This　paper　will　struggle　to　tackle　the　problem　by　comparing　the　electrochemical　behaviors　of　tungsten　ions　from　the　electrochemical　dissolution　of　tungsten　carbide　and　NaCl-KCl-2　wt%　Na2WO4　melt.　The　electrochemical　method　had　been　investigated　as　a　mean　to　understand　the　fundamental　thermodynamic　and　mass　transport　properties　of　tungsten　ions.　The　apparent　standard　potentials　of　oxidation　and　reduction　couple　at　several　temperatures　were　calculated　by　using　a　proposed　new　method.　The　diffusion　coefficients　of　tungsten　ions　were　determined.　It　can　be　concluded　that　the　tungsten　ions　in　the　molten　salt　after　tungsten　carbide　electrolysis　were　simple　ions　without　coordinating　anions　by　comparing　the　dynamics　and　thermodynamic　calculation　results　of　the　two　systems.　The　developed　simulation　boxes　can　serve　as　a　verification　for　further　theoretical　investigations　of　the　coordination　form　of　tungsten　ion　groups　at　molecular　scale.　The　results　of　this　work　provide　necessary　knowledge　for　the　development　methods　to　determine　the　dynamics　and　thermodynamic　properties　and　coordination　forms　of　metal　ions.　(C)　2021　Elsevier　B.V.　All　rights　reserved.