Can somebody explain me the electrolysis of molten $\ce{NaCl}$ via electrode potential?

Reduction potential of $\ce{Cl-}$ is -1.36 V, while sodium metal is -2.76 V, but still sodium is reduced and not $\ce{Cl-}.$

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    $\begingroup$ Cl- can't be reduced. What is dead may never die, they say. Same story here. $\endgroup$ Aug 29, 2019 at 9:42
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    $\begingroup$ @andselisk, random capitalization is a typical writing problem among South Asians. I see this everyday. There is no concept of capital letters in the alphabetical system and definite articles. $\endgroup$
    – AChem
    Aug 29, 2019 at 12:59
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    $\begingroup$ @M.Farooq Oh, thank you, I wasn't aware of that. How interesting. $\endgroup$
    – andselisk
    Aug 29, 2019 at 13:09

1 Answer 1


The misconception you have in the question is that the concept of tabulated electrode potentials do not apply to molten salts. The values in general chemistry textbooks have been calculated in water under specific concentrations. No need to extrapolate electrode potentials to molten states.

  • $\begingroup$ True, but there is a much deeper misconception which (IMHO) has to be dealt with first. I mean, the basic idea of what can and what can't be reduced. $\endgroup$ Aug 29, 2019 at 13:20
  • $\begingroup$ I think the student is connecting reduction potentials as "reduction only" potentials. $\endgroup$
    – AChem
    Aug 29, 2019 at 13:51

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