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Determination of solubility equilibrium using galvanic cell reactions


How do I calculate the cell voltage using the following half-reactions and solubility products?Zn-Cu galvanic cellHow to calculate galvanic cell spontaneity?Galvanic cell chemistryHow to calculate the electromotive force of a silver chloride/ silver bromide cell?Galvanic cell structure and functionequilibrium state of a galvanic cellelectrochemical (Galvanic) cell solution purposeSalt bridge in galvanic cellSolubility equilibrium













4












$begingroup$


This is the problem:



We can determine the solubility equilibrium for silver bromide using cell:



Ag (s) | AgNO3 (aq) || KBr (aq) | AgBr (s) | Ag (s)



We know that:



$textAgBr + texte^- rightarrow textAg + textBr^- textE^0=0.095 textV$



$textAg^+ + texte^- rightarrow textAg textE^0=0.799 textV$



First of all isn't that cell diagram incorrect? As far as I understand it is the silver reducing from silver nitrate to metallic silver thus being cathode. And vice versa for the silver bromide that is being produced more as silver is oxidating. Shouldn't the cell diagram be like this instead:



KBr (aq) | AgBr (s) | Ag (s) || Ag (s) | AgNO3 (aq)



Anyways, if we consider the Nernst equation:



$$E = E_0-fracRTnFlnk$$



and assume that the galvanic cell is in equilibrium when there is no voltage (i.e. $E=0$). We can then write:



$$lnk=fracE^0nFRT \ leftrightarrow k=e^fracE^0nFRT$$



Then plug in the numbers:



$$lnk=frac(-0.095+0.799) textVcdot 1 textmolcdot 96485.31 fractextCtextmol8.31451 fractextJtextmolcdot textKcdot 293.15 textK \ leftrightarrow
k= 1.26754cdot 10^12$$



But the right answer is:



$$1.26 cdot 10^-12 textmol^2/textdm^6$$



Any ideas what am I doing wrong?










share|improve this question







New contributor




nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
Check out our Code of Conduct.







$endgroup$
















    4












    $begingroup$


    This is the problem:



    We can determine the solubility equilibrium for silver bromide using cell:



    Ag (s) | AgNO3 (aq) || KBr (aq) | AgBr (s) | Ag (s)



    We know that:



    $textAgBr + texte^- rightarrow textAg + textBr^- textE^0=0.095 textV$



    $textAg^+ + texte^- rightarrow textAg textE^0=0.799 textV$



    First of all isn't that cell diagram incorrect? As far as I understand it is the silver reducing from silver nitrate to metallic silver thus being cathode. And vice versa for the silver bromide that is being produced more as silver is oxidating. Shouldn't the cell diagram be like this instead:



    KBr (aq) | AgBr (s) | Ag (s) || Ag (s) | AgNO3 (aq)



    Anyways, if we consider the Nernst equation:



    $$E = E_0-fracRTnFlnk$$



    and assume that the galvanic cell is in equilibrium when there is no voltage (i.e. $E=0$). We can then write:



    $$lnk=fracE^0nFRT \ leftrightarrow k=e^fracE^0nFRT$$



    Then plug in the numbers:



    $$lnk=frac(-0.095+0.799) textVcdot 1 textmolcdot 96485.31 fractextCtextmol8.31451 fractextJtextmolcdot textKcdot 293.15 textK \ leftrightarrow
    k= 1.26754cdot 10^12$$



    But the right answer is:



    $$1.26 cdot 10^-12 textmol^2/textdm^6$$



    Any ideas what am I doing wrong?










    share|improve this question







    New contributor




    nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
    Check out our Code of Conduct.







    $endgroup$














      4












      4








      4





      $begingroup$


      This is the problem:



      We can determine the solubility equilibrium for silver bromide using cell:



      Ag (s) | AgNO3 (aq) || KBr (aq) | AgBr (s) | Ag (s)



      We know that:



      $textAgBr + texte^- rightarrow textAg + textBr^- textE^0=0.095 textV$



      $textAg^+ + texte^- rightarrow textAg textE^0=0.799 textV$



      First of all isn't that cell diagram incorrect? As far as I understand it is the silver reducing from silver nitrate to metallic silver thus being cathode. And vice versa for the silver bromide that is being produced more as silver is oxidating. Shouldn't the cell diagram be like this instead:



      KBr (aq) | AgBr (s) | Ag (s) || Ag (s) | AgNO3 (aq)



      Anyways, if we consider the Nernst equation:



      $$E = E_0-fracRTnFlnk$$



      and assume that the galvanic cell is in equilibrium when there is no voltage (i.e. $E=0$). We can then write:



      $$lnk=fracE^0nFRT \ leftrightarrow k=e^fracE^0nFRT$$



      Then plug in the numbers:



      $$lnk=frac(-0.095+0.799) textVcdot 1 textmolcdot 96485.31 fractextCtextmol8.31451 fractextJtextmolcdot textKcdot 293.15 textK \ leftrightarrow
      k= 1.26754cdot 10^12$$



      But the right answer is:



      $$1.26 cdot 10^-12 textmol^2/textdm^6$$



      Any ideas what am I doing wrong?










      share|improve this question







      New contributor




      nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
      Check out our Code of Conduct.







      $endgroup$




      This is the problem:



      We can determine the solubility equilibrium for silver bromide using cell:



      Ag (s) | AgNO3 (aq) || KBr (aq) | AgBr (s) | Ag (s)



      We know that:



      $textAgBr + texte^- rightarrow textAg + textBr^- textE^0=0.095 textV$



      $textAg^+ + texte^- rightarrow textAg textE^0=0.799 textV$



      First of all isn't that cell diagram incorrect? As far as I understand it is the silver reducing from silver nitrate to metallic silver thus being cathode. And vice versa for the silver bromide that is being produced more as silver is oxidating. Shouldn't the cell diagram be like this instead:



      KBr (aq) | AgBr (s) | Ag (s) || Ag (s) | AgNO3 (aq)



      Anyways, if we consider the Nernst equation:



      $$E = E_0-fracRTnFlnk$$



      and assume that the galvanic cell is in equilibrium when there is no voltage (i.e. $E=0$). We can then write:



      $$lnk=fracE^0nFRT \ leftrightarrow k=e^fracE^0nFRT$$



      Then plug in the numbers:



      $$lnk=frac(-0.095+0.799) textVcdot 1 textmolcdot 96485.31 fractextCtextmol8.31451 fractextJtextmolcdot textKcdot 293.15 textK \ leftrightarrow
      k= 1.26754cdot 10^12$$



      But the right answer is:



      $$1.26 cdot 10^-12 textmol^2/textdm^6$$



      Any ideas what am I doing wrong?







      electrochemistry solubility






      share|improve this question







      New contributor




      nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
      Check out our Code of Conduct.











      share|improve this question







      New contributor




      nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
      Check out our Code of Conduct.









      share|improve this question




      share|improve this question






      New contributor




      nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
      Check out our Code of Conduct.









      asked 11 hours ago









      nh3nh3

      232




      232




      New contributor




      nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
      Check out our Code of Conduct.





      New contributor





      nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
      Check out our Code of Conduct.






      nh3 is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
      Check out our Code of Conduct.




















          2 Answers
          2






          active

          oldest

          votes


















          4












          $begingroup$

          The leftmost and rightmost parts of the galvanic cell notation are supposed to be electrodes, not electrolytes (no KBr (aq) and the likes of it there). What is more, the double vertical line represents the interface where the junction potential has been eliminated ((c) Atkins), i.e. salt bridge, which in this case is the interface between electrolytes. The left hand side of the cell is anode, where the oxidation occurs, and the silver ions are reduced at the cathode, which is written on the right hand side. It seems to me that the correct notation is:



          Ag (s) | AgBr (s) | KBr (aq) || AgNO3 (aq) | Ag (s)



          In turn, the cell reaction is $ceAg+ + Br- -> AgBr$, and the EMF of this reaction is +0.704 V. It is not surprising that the equilibrium constant of this reaction is much larger than unity, otherwise silver bromide wouldn't be so stable and so insoluble. What you're missing is that the solubility product, which you want to calculate, is an equilibrium constant of the inverse process - not the formation, but the dissolution of $ceAgBr$. So take the inverse of the equilibrium constant which you obtained from the galvanic cell EMF, and you'll get $7.9cdot10^-13$, which is pretty close to the reference values.






          share|improve this answer









          $endgroup$




















            3












            $begingroup$

            Consider the net reaction you are looking at:



            $$ceAg+ + Br- -> AgBr, E^circ = 0.704 mathrmV$$



            The equilibrium, not surprisingly, lies to the right, which we can tell from the standard potential and from knowledge about the solubility of silver bromide.



            This means that you expect the concentrations of reactants to be quite small. When they then go into the equilibrium constant, I expect a very large equilibrium constant. In other words, your answer is much more consistent with the chemical situation than the expected answer, based solely on the magnitude of the two answers.






            share|improve this answer









            $endgroup$












              Your Answer





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              2 Answers
              2






              active

              oldest

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              2 Answers
              2






              active

              oldest

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              active

              oldest

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              active

              oldest

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              4












              $begingroup$

              The leftmost and rightmost parts of the galvanic cell notation are supposed to be electrodes, not electrolytes (no KBr (aq) and the likes of it there). What is more, the double vertical line represents the interface where the junction potential has been eliminated ((c) Atkins), i.e. salt bridge, which in this case is the interface between electrolytes. The left hand side of the cell is anode, where the oxidation occurs, and the silver ions are reduced at the cathode, which is written on the right hand side. It seems to me that the correct notation is:



              Ag (s) | AgBr (s) | KBr (aq) || AgNO3 (aq) | Ag (s)



              In turn, the cell reaction is $ceAg+ + Br- -> AgBr$, and the EMF of this reaction is +0.704 V. It is not surprising that the equilibrium constant of this reaction is much larger than unity, otherwise silver bromide wouldn't be so stable and so insoluble. What you're missing is that the solubility product, which you want to calculate, is an equilibrium constant of the inverse process - not the formation, but the dissolution of $ceAgBr$. So take the inverse of the equilibrium constant which you obtained from the galvanic cell EMF, and you'll get $7.9cdot10^-13$, which is pretty close to the reference values.






              share|improve this answer









              $endgroup$

















                4












                $begingroup$

                The leftmost and rightmost parts of the galvanic cell notation are supposed to be electrodes, not electrolytes (no KBr (aq) and the likes of it there). What is more, the double vertical line represents the interface where the junction potential has been eliminated ((c) Atkins), i.e. salt bridge, which in this case is the interface between electrolytes. The left hand side of the cell is anode, where the oxidation occurs, and the silver ions are reduced at the cathode, which is written on the right hand side. It seems to me that the correct notation is:



                Ag (s) | AgBr (s) | KBr (aq) || AgNO3 (aq) | Ag (s)



                In turn, the cell reaction is $ceAg+ + Br- -> AgBr$, and the EMF of this reaction is +0.704 V. It is not surprising that the equilibrium constant of this reaction is much larger than unity, otherwise silver bromide wouldn't be so stable and so insoluble. What you're missing is that the solubility product, which you want to calculate, is an equilibrium constant of the inverse process - not the formation, but the dissolution of $ceAgBr$. So take the inverse of the equilibrium constant which you obtained from the galvanic cell EMF, and you'll get $7.9cdot10^-13$, which is pretty close to the reference values.






                share|improve this answer









                $endgroup$















                  4












                  4








                  4





                  $begingroup$

                  The leftmost and rightmost parts of the galvanic cell notation are supposed to be electrodes, not electrolytes (no KBr (aq) and the likes of it there). What is more, the double vertical line represents the interface where the junction potential has been eliminated ((c) Atkins), i.e. salt bridge, which in this case is the interface between electrolytes. The left hand side of the cell is anode, where the oxidation occurs, and the silver ions are reduced at the cathode, which is written on the right hand side. It seems to me that the correct notation is:



                  Ag (s) | AgBr (s) | KBr (aq) || AgNO3 (aq) | Ag (s)



                  In turn, the cell reaction is $ceAg+ + Br- -> AgBr$, and the EMF of this reaction is +0.704 V. It is not surprising that the equilibrium constant of this reaction is much larger than unity, otherwise silver bromide wouldn't be so stable and so insoluble. What you're missing is that the solubility product, which you want to calculate, is an equilibrium constant of the inverse process - not the formation, but the dissolution of $ceAgBr$. So take the inverse of the equilibrium constant which you obtained from the galvanic cell EMF, and you'll get $7.9cdot10^-13$, which is pretty close to the reference values.






                  share|improve this answer









                  $endgroup$



                  The leftmost and rightmost parts of the galvanic cell notation are supposed to be electrodes, not electrolytes (no KBr (aq) and the likes of it there). What is more, the double vertical line represents the interface where the junction potential has been eliminated ((c) Atkins), i.e. salt bridge, which in this case is the interface between electrolytes. The left hand side of the cell is anode, where the oxidation occurs, and the silver ions are reduced at the cathode, which is written on the right hand side. It seems to me that the correct notation is:



                  Ag (s) | AgBr (s) | KBr (aq) || AgNO3 (aq) | Ag (s)



                  In turn, the cell reaction is $ceAg+ + Br- -> AgBr$, and the EMF of this reaction is +0.704 V. It is not surprising that the equilibrium constant of this reaction is much larger than unity, otherwise silver bromide wouldn't be so stable and so insoluble. What you're missing is that the solubility product, which you want to calculate, is an equilibrium constant of the inverse process - not the formation, but the dissolution of $ceAgBr$. So take the inverse of the equilibrium constant which you obtained from the galvanic cell EMF, and you'll get $7.9cdot10^-13$, which is pretty close to the reference values.







                  share|improve this answer












                  share|improve this answer



                  share|improve this answer










                  answered 10 hours ago









                  voffchvoffch

                  5887




                  5887





















                      3












                      $begingroup$

                      Consider the net reaction you are looking at:



                      $$ceAg+ + Br- -> AgBr, E^circ = 0.704 mathrmV$$



                      The equilibrium, not surprisingly, lies to the right, which we can tell from the standard potential and from knowledge about the solubility of silver bromide.



                      This means that you expect the concentrations of reactants to be quite small. When they then go into the equilibrium constant, I expect a very large equilibrium constant. In other words, your answer is much more consistent with the chemical situation than the expected answer, based solely on the magnitude of the two answers.






                      share|improve this answer









                      $endgroup$

















                        3












                        $begingroup$

                        Consider the net reaction you are looking at:



                        $$ceAg+ + Br- -> AgBr, E^circ = 0.704 mathrmV$$



                        The equilibrium, not surprisingly, lies to the right, which we can tell from the standard potential and from knowledge about the solubility of silver bromide.



                        This means that you expect the concentrations of reactants to be quite small. When they then go into the equilibrium constant, I expect a very large equilibrium constant. In other words, your answer is much more consistent with the chemical situation than the expected answer, based solely on the magnitude of the two answers.






                        share|improve this answer









                        $endgroup$















                          3












                          3








                          3





                          $begingroup$

                          Consider the net reaction you are looking at:



                          $$ceAg+ + Br- -> AgBr, E^circ = 0.704 mathrmV$$



                          The equilibrium, not surprisingly, lies to the right, which we can tell from the standard potential and from knowledge about the solubility of silver bromide.



                          This means that you expect the concentrations of reactants to be quite small. When they then go into the equilibrium constant, I expect a very large equilibrium constant. In other words, your answer is much more consistent with the chemical situation than the expected answer, based solely on the magnitude of the two answers.






                          share|improve this answer









                          $endgroup$



                          Consider the net reaction you are looking at:



                          $$ceAg+ + Br- -> AgBr, E^circ = 0.704 mathrmV$$



                          The equilibrium, not surprisingly, lies to the right, which we can tell from the standard potential and from knowledge about the solubility of silver bromide.



                          This means that you expect the concentrations of reactants to be quite small. When they then go into the equilibrium constant, I expect a very large equilibrium constant. In other words, your answer is much more consistent with the chemical situation than the expected answer, based solely on the magnitude of the two answers.







                          share|improve this answer












                          share|improve this answer



                          share|improve this answer










                          answered 11 hours ago









                          ZheZhe

                          12.8k12550




                          12.8k12550




















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