If oxygen is more electronegative why doesn't it replace chlorine in compounds?


$\ce{2NaBr + Cl2 -> 2NaCl + Br2}$

works, while

$\ce{4NaCl + O2 -> 2Na2O + 2Cl2}$



You can displace chlorine from hydrogen chloride.

With sodium chloride, if you did form sodium oxide it would be a strong base. As such it extracts a $\ce{Cl^+}$ moiety from any potential chlorine molecules. Sodium chloride is oxidized by oxygen, but the oxidized chlorine ends up as hypochlorite oxyanions such hypochlorite (i.e., oxide coordinated to chlorine).

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  • $\begingroup$ It's redox not acid base. $\endgroup$ – Mithoron Feb 10 '18 at 17:37
  • $\begingroup$ Why would it not be both? $\endgroup$ – Oscar Lanzi Feb 10 '18 at 17:38
  • $\begingroup$ I'm still not sure what you even mean in this. Proper answer is that O2 has to low redox potential. $\endgroup$ – Mithoron Feb 10 '18 at 17:43
  • $\begingroup$ Then say so in your own answer. $\endgroup$ – Oscar Lanzi Feb 10 '18 at 18:45
  • $\begingroup$ Re: "chlorine gets oxidized to oxyanions such hypochlorite" So, the products formed from $\ce{Na2O\+Cl2}$ are $\ce{NaCl\+NaOCl}$? Thanks! $\endgroup$ – Gaurang Tandon Feb 13 '18 at 4:43

In order to know if a reaction is spontaneous or not (if it will happen towards the direction you have drawn it) you must look at its Gibbs energy, ΔG. Electronegativity of one element in a reaction is one of the many factors that contribute to it. In this case you are dealing with a redox reaction (because the oxidation states of the elements involved change) and therefore you need to use the relationship: ΔG=-nFE$^0$cell with E$^0$cell calculated from the relevant half reactions. For more details read an introduction to electrochemistry from some inorganic chemistry book.

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