Why does electrolysis of aqueous concentrated sodium bromide produce bromine at the anode? Announcing the arrival of Valued Associate #679: Cesar Manara Planned maintenance scheduled April 23, 2019 at 23:30 UTC (7:30pm US/Eastern) 2019 Moderator Election Q&A - Question CollectionElectrolysis on aqeuous solutionElectrolysis in aqueous solution – which equations to use to predict product at each electrode?While electrolyzing concentrated aqueous sodium chloride, why is it that chlorine is discharged but not sodium?Reaction of sulfate ion in copper sulfate electrolysisDissociation of zinc anode during electrolysisElectrolysis of concentrated NaClElectrolysis of water - why not pure water?Why is bromine produced at the anode when aqueous sodium bromide undergoes electrolysis?How does pH change during the electrolysis of water?Does electrolysis of aqueous tin(II) chloride produce Cl₂, SnCl₄ or both?

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Why does electrolysis of aqueous concentrated sodium bromide produce bromine at the anode?



Announcing the arrival of Valued Associate #679: Cesar Manara
Planned maintenance scheduled April 23, 2019 at 23:30 UTC (7:30pm US/Eastern)
2019 Moderator Election Q&A - Question CollectionElectrolysis on aqeuous solutionElectrolysis in aqueous solution – which equations to use to predict product at each electrode?While electrolyzing concentrated aqueous sodium chloride, why is it that chlorine is discharged but not sodium?Reaction of sulfate ion in copper sulfate electrolysisDissociation of zinc anode during electrolysisElectrolysis of concentrated NaClElectrolysis of water - why not pure water?Why is bromine produced at the anode when aqueous sodium bromide undergoes electrolysis?How does pH change during the electrolysis of water?Does electrolysis of aqueous tin(II) chloride produce Cl₂, SnCl₄ or both?










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$begingroup$


It is often stated that electrolysis of any aqueous concentrated halogen compound will produce the halogen at the anode, despite it having a more postitive standard electrode potential than the oxidation of hydroxide, while when it is dilute oxygen will be produced, but what is the reason for this?



Why does the principle of concentrated solutions during electrolysis only apply for halogens and not any other element. For example, why isn’t sodium produced at the cathode when concentrated sodium chloride is electrolysed?










share|improve this question









$endgroup$
















    7












    $begingroup$


    It is often stated that electrolysis of any aqueous concentrated halogen compound will produce the halogen at the anode, despite it having a more postitive standard electrode potential than the oxidation of hydroxide, while when it is dilute oxygen will be produced, but what is the reason for this?



    Why does the principle of concentrated solutions during electrolysis only apply for halogens and not any other element. For example, why isn’t sodium produced at the cathode when concentrated sodium chloride is electrolysed?










    share|improve this question









    $endgroup$














      7












      7








      7





      $begingroup$


      It is often stated that electrolysis of any aqueous concentrated halogen compound will produce the halogen at the anode, despite it having a more postitive standard electrode potential than the oxidation of hydroxide, while when it is dilute oxygen will be produced, but what is the reason for this?



      Why does the principle of concentrated solutions during electrolysis only apply for halogens and not any other element. For example, why isn’t sodium produced at the cathode when concentrated sodium chloride is electrolysed?










      share|improve this question









      $endgroup$




      It is often stated that electrolysis of any aqueous concentrated halogen compound will produce the halogen at the anode, despite it having a more postitive standard electrode potential than the oxidation of hydroxide, while when it is dilute oxygen will be produced, but what is the reason for this?



      Why does the principle of concentrated solutions during electrolysis only apply for halogens and not any other element. For example, why isn’t sodium produced at the cathode when concentrated sodium chloride is electrolysed?







      electrolysis






      share|improve this question













      share|improve this question











      share|improve this question




      share|improve this question










      asked 2 days ago









      Anthony PAnthony P

      572




      572




















          1 Answer
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          9












          $begingroup$

          There is important to know the actual potential depends on actual activities of reagents ( approximately concentrations for dilute solutions).



          Additionally, the electrode potential is the thermodynamic quantity. If some net reaction kinetic is involved, other potentials affects the actual potential at the solution border, like the diffusion potential and dielectric layer potential.



          We consider reactions
          $$beginalign
          ceBr2 + 2e- &<=> 2 Br-\
          ceO2 + 2 H2O + 4e- &<=> 4 OH-\
          endalign$$



          The initial bromine activity is very low.



          Activity/concentration ratio of ions typically decreases with concentration, as seen in the Debye-Huckel equation,
          but for high salt concentrations it often jumps up the roof.



          Therefore, activity of bromides is very high and the actual potential gets low.



          $$E_c_ceBr2/c_ceBr-=E^circ_c_ceBr2/c_ceBr- + 0.059 log left( fraca_ceBr2a_ceBr-right)$$



          OTOH,
          The potential for hydroxide oxidation is pushed up for neutral solutions to the middle between standard redox potentials for acidic and alkaline solutions $$(+0.401 + +1.229)/2=+0.815$$



          $$E_c_ceO2/c_ceOH-=E^circ_c_ceO2/c_ceOH- + 0.059log left( fraca_ceO2a_ceOH-right)$$




          For $ceNaCl$ solutions, difference of standard potentials is too high to produce metallic sodium, unless one uses mercury as the cathode, where happens the hydrogen, related to its reaction kinetics. This is used for production of sodium hydroxide, where sodium amalgam reacts with water.






          share|improve this answer











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            1 Answer
            1






            active

            oldest

            votes









            active

            oldest

            votes






            active

            oldest

            votes









            9












            $begingroup$

            There is important to know the actual potential depends on actual activities of reagents ( approximately concentrations for dilute solutions).



            Additionally, the electrode potential is the thermodynamic quantity. If some net reaction kinetic is involved, other potentials affects the actual potential at the solution border, like the diffusion potential and dielectric layer potential.



            We consider reactions
            $$beginalign
            ceBr2 + 2e- &<=> 2 Br-\
            ceO2 + 2 H2O + 4e- &<=> 4 OH-\
            endalign$$



            The initial bromine activity is very low.



            Activity/concentration ratio of ions typically decreases with concentration, as seen in the Debye-Huckel equation,
            but for high salt concentrations it often jumps up the roof.



            Therefore, activity of bromides is very high and the actual potential gets low.



            $$E_c_ceBr2/c_ceBr-=E^circ_c_ceBr2/c_ceBr- + 0.059 log left( fraca_ceBr2a_ceBr-right)$$



            OTOH,
            The potential for hydroxide oxidation is pushed up for neutral solutions to the middle between standard redox potentials for acidic and alkaline solutions $$(+0.401 + +1.229)/2=+0.815$$



            $$E_c_ceO2/c_ceOH-=E^circ_c_ceO2/c_ceOH- + 0.059log left( fraca_ceO2a_ceOH-right)$$




            For $ceNaCl$ solutions, difference of standard potentials is too high to produce metallic sodium, unless one uses mercury as the cathode, where happens the hydrogen, related to its reaction kinetics. This is used for production of sodium hydroxide, where sodium amalgam reacts with water.






            share|improve this answer











            $endgroup$

















              9












              $begingroup$

              There is important to know the actual potential depends on actual activities of reagents ( approximately concentrations for dilute solutions).



              Additionally, the electrode potential is the thermodynamic quantity. If some net reaction kinetic is involved, other potentials affects the actual potential at the solution border, like the diffusion potential and dielectric layer potential.



              We consider reactions
              $$beginalign
              ceBr2 + 2e- &<=> 2 Br-\
              ceO2 + 2 H2O + 4e- &<=> 4 OH-\
              endalign$$



              The initial bromine activity is very low.



              Activity/concentration ratio of ions typically decreases with concentration, as seen in the Debye-Huckel equation,
              but for high salt concentrations it often jumps up the roof.



              Therefore, activity of bromides is very high and the actual potential gets low.



              $$E_c_ceBr2/c_ceBr-=E^circ_c_ceBr2/c_ceBr- + 0.059 log left( fraca_ceBr2a_ceBr-right)$$



              OTOH,
              The potential for hydroxide oxidation is pushed up for neutral solutions to the middle between standard redox potentials for acidic and alkaline solutions $$(+0.401 + +1.229)/2=+0.815$$



              $$E_c_ceO2/c_ceOH-=E^circ_c_ceO2/c_ceOH- + 0.059log left( fraca_ceO2a_ceOH-right)$$




              For $ceNaCl$ solutions, difference of standard potentials is too high to produce metallic sodium, unless one uses mercury as the cathode, where happens the hydrogen, related to its reaction kinetics. This is used for production of sodium hydroxide, where sodium amalgam reacts with water.






              share|improve this answer











              $endgroup$















                9












                9








                9





                $begingroup$

                There is important to know the actual potential depends on actual activities of reagents ( approximately concentrations for dilute solutions).



                Additionally, the electrode potential is the thermodynamic quantity. If some net reaction kinetic is involved, other potentials affects the actual potential at the solution border, like the diffusion potential and dielectric layer potential.



                We consider reactions
                $$beginalign
                ceBr2 + 2e- &<=> 2 Br-\
                ceO2 + 2 H2O + 4e- &<=> 4 OH-\
                endalign$$



                The initial bromine activity is very low.



                Activity/concentration ratio of ions typically decreases with concentration, as seen in the Debye-Huckel equation,
                but for high salt concentrations it often jumps up the roof.



                Therefore, activity of bromides is very high and the actual potential gets low.



                $$E_c_ceBr2/c_ceBr-=E^circ_c_ceBr2/c_ceBr- + 0.059 log left( fraca_ceBr2a_ceBr-right)$$



                OTOH,
                The potential for hydroxide oxidation is pushed up for neutral solutions to the middle between standard redox potentials for acidic and alkaline solutions $$(+0.401 + +1.229)/2=+0.815$$



                $$E_c_ceO2/c_ceOH-=E^circ_c_ceO2/c_ceOH- + 0.059log left( fraca_ceO2a_ceOH-right)$$




                For $ceNaCl$ solutions, difference of standard potentials is too high to produce metallic sodium, unless one uses mercury as the cathode, where happens the hydrogen, related to its reaction kinetics. This is used for production of sodium hydroxide, where sodium amalgam reacts with water.






                share|improve this answer











                $endgroup$



                There is important to know the actual potential depends on actual activities of reagents ( approximately concentrations for dilute solutions).



                Additionally, the electrode potential is the thermodynamic quantity. If some net reaction kinetic is involved, other potentials affects the actual potential at the solution border, like the diffusion potential and dielectric layer potential.



                We consider reactions
                $$beginalign
                ceBr2 + 2e- &<=> 2 Br-\
                ceO2 + 2 H2O + 4e- &<=> 4 OH-\
                endalign$$



                The initial bromine activity is very low.



                Activity/concentration ratio of ions typically decreases with concentration, as seen in the Debye-Huckel equation,
                but for high salt concentrations it often jumps up the roof.



                Therefore, activity of bromides is very high and the actual potential gets low.



                $$E_c_ceBr2/c_ceBr-=E^circ_c_ceBr2/c_ceBr- + 0.059 log left( fraca_ceBr2a_ceBr-right)$$



                OTOH,
                The potential for hydroxide oxidation is pushed up for neutral solutions to the middle between standard redox potentials for acidic and alkaline solutions $$(+0.401 + +1.229)/2=+0.815$$



                $$E_c_ceO2/c_ceOH-=E^circ_c_ceO2/c_ceOH- + 0.059log left( fraca_ceO2a_ceOH-right)$$




                For $ceNaCl$ solutions, difference of standard potentials is too high to produce metallic sodium, unless one uses mercury as the cathode, where happens the hydrogen, related to its reaction kinetics. This is used for production of sodium hydroxide, where sodium amalgam reacts with water.







                share|improve this answer














                share|improve this answer



                share|improve this answer








                edited 2 days ago

























                answered 2 days ago









                PoutnikPoutnik

                1,494311




                1,494311



























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