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No sign flipping while figuring out the emf of voltaic cell?


Half cell method of voltage calculation in an electrochemical cellFinding concentrations in a voltaic cellWhy does the anode solution contain Sn2+ in a Sn-Cu voltaic cell?Can the thermodynamic predictions of redox reactions based on E and dG contradict each other?Explain the difference in stability of permanganate ions in acidic/ alkaline solutions?At what voltage does the electrodeposition of the metal start?Positive electrode of an electrochemical cell?Do I use the Nernst equation when the concentrations of electrolyte in both half cells are equal?Does silver oxidise in a pH 1 solution?How can we directly add half cell potentials to measure the EMF of a galvanic cell?













3












$begingroup$


I learnt that for a voltaic cell, the value for the $E_textcell^circ$ when the reaction is spontaneous is given by



$$E_textcell^circ = E_textcathode^circ - E_textanode^circ, labeleqn:1tag1$$



so that the difference in the right gives us a positive value for $E_textcell^circ$.



But suppose we are given two half-reactions:



$$
beginalign
ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
endalign
$$



When finding the overall spontaneous reaction, we must flip the second reaction, multiply it by $2$, and then add it with the first to get our desired equation.




But when determining the $E_textcell^circ$, why don't we negate the minus sign of the second half-reaction and make positive, before we put it in $eqrefeqn:1$ to figure out the $E_textcell^circ$? Shouldn't we do that because we reversed the second equation?



My book tells me to keep the $E_texthalf-cells^circ$ as they are written in the tables and simply put them in $eqrefeqn:1$. But why?










share|improve this question











$endgroup$
















    3












    $begingroup$


    I learnt that for a voltaic cell, the value for the $E_textcell^circ$ when the reaction is spontaneous is given by



    $$E_textcell^circ = E_textcathode^circ - E_textanode^circ, labeleqn:1tag1$$



    so that the difference in the right gives us a positive value for $E_textcell^circ$.



    But suppose we are given two half-reactions:



    $$
    beginalign
    ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
    ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
    endalign
    $$



    When finding the overall spontaneous reaction, we must flip the second reaction, multiply it by $2$, and then add it with the first to get our desired equation.




    But when determining the $E_textcell^circ$, why don't we negate the minus sign of the second half-reaction and make positive, before we put it in $eqrefeqn:1$ to figure out the $E_textcell^circ$? Shouldn't we do that because we reversed the second equation?



    My book tells me to keep the $E_texthalf-cells^circ$ as they are written in the tables and simply put them in $eqrefeqn:1$. But why?










    share|improve this question











    $endgroup$














      3












      3








      3





      $begingroup$


      I learnt that for a voltaic cell, the value for the $E_textcell^circ$ when the reaction is spontaneous is given by



      $$E_textcell^circ = E_textcathode^circ - E_textanode^circ, labeleqn:1tag1$$



      so that the difference in the right gives us a positive value for $E_textcell^circ$.



      But suppose we are given two half-reactions:



      $$
      beginalign
      ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
      ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
      endalign
      $$



      When finding the overall spontaneous reaction, we must flip the second reaction, multiply it by $2$, and then add it with the first to get our desired equation.




      But when determining the $E_textcell^circ$, why don't we negate the minus sign of the second half-reaction and make positive, before we put it in $eqrefeqn:1$ to figure out the $E_textcell^circ$? Shouldn't we do that because we reversed the second equation?



      My book tells me to keep the $E_texthalf-cells^circ$ as they are written in the tables and simply put them in $eqrefeqn:1$. But why?










      share|improve this question











      $endgroup$




      I learnt that for a voltaic cell, the value for the $E_textcell^circ$ when the reaction is spontaneous is given by



      $$E_textcell^circ = E_textcathode^circ - E_textanode^circ, labeleqn:1tag1$$



      so that the difference in the right gives us a positive value for $E_textcell^circ$.



      But suppose we are given two half-reactions:



      $$
      beginalign
      ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
      ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
      endalign
      $$



      When finding the overall spontaneous reaction, we must flip the second reaction, multiply it by $2$, and then add it with the first to get our desired equation.




      But when determining the $E_textcell^circ$, why don't we negate the minus sign of the second half-reaction and make positive, before we put it in $eqrefeqn:1$ to figure out the $E_textcell^circ$? Shouldn't we do that because we reversed the second equation?



      My book tells me to keep the $E_texthalf-cells^circ$ as they are written in the tables and simply put them in $eqrefeqn:1$. But why?







      physical-chemistry electrochemistry redox






      share|improve this question















      share|improve this question













      share|improve this question




      share|improve this question








      edited Mar 30 at 13:10







      Apekshik Panigrahi

















      asked Mar 30 at 12:25









      Apekshik PanigrahiApekshik Panigrahi

      1505




      1505




















          3 Answers
          3






          active

          oldest

          votes


















          2












          $begingroup$

          Take a look at the two half reactions:



          $$
          beginalign
          ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
          ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
          endalign
          $$



          If there is an electron for grabs (like the ones in the wire of a voltaic cell), $ceAg+(aq)$ and $ceSn^2+(aq)$ are competing for it. Whichever half reaction has the higher (more positive) reduction potential will win. If the reduction potentials are equal, it is a draw and the reaction is at equilibrium. So we are taking the difference of the reduction potentials to see in which direction the reaction will go.




          No sign flipping while figuring out the emf of voltaic cell?




          Take a look at the equation you are using to figure out the emf. You are already treating the oxidation half reaction differently than the reduction half reaction because there is a negative sign in front of the anode reduction potential.



          $$E_textcell^circ = E_textcathode^circ - E_textanode^circ$$



          If you switch the anode and cathode half reaction, you would get the opposite sign for the emf. (Not that the reaction would go in that direction.)






          share|improve this answer









          $endgroup$




















            2












            $begingroup$


            My book tells me to keep the E∘half-cells as they are written in the
            tables and simply put them in




            Your book is then one of the few books which teaches electrochemistry properly. The sign of the electrode reduction potential is invariant. If reflects the sign of the electrostatic charge of the electrode with respect to hydrogen electrode. I don;t know if you like history or not, long time ago in the 1950s-60s showing the electrostatic sign of a cell by means of a specially designed electroscope was a standard experiment in physics.



            Imagine if I say H2O (l) --> H2O (g) at 100 oC



            Does this mean reversing the reaction



            H2O(g) --> H2O (l) will be at -100 oC?



            You can see logical fallacy in reversing the sign of electrode potentials.



            Yes, there was a lot of confusion in electrode signs for more than 100 years but now it has been sorted out.






            share|improve this answer









            $endgroup$




















              1












              $begingroup$

              The Nernst equation and electrochemical potentials relate to redox systems, not to reagents and products. The forward and reversed reactions are the same redox system.



              Imagine you would want to make a galvanical cell with the same electrodes. Flipping the sign would grant you a Nobel price for inventing a perpetuum mobile.






              share|improve this answer









              $endgroup$













                Your Answer








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                3 Answers
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                active

                oldest

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                3 Answers
                3






                active

                oldest

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                active

                oldest

                votes






                active

                oldest

                votes









                2












                $begingroup$

                Take a look at the two half reactions:



                $$
                beginalign
                ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
                ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
                endalign
                $$



                If there is an electron for grabs (like the ones in the wire of a voltaic cell), $ceAg+(aq)$ and $ceSn^2+(aq)$ are competing for it. Whichever half reaction has the higher (more positive) reduction potential will win. If the reduction potentials are equal, it is a draw and the reaction is at equilibrium. So we are taking the difference of the reduction potentials to see in which direction the reaction will go.




                No sign flipping while figuring out the emf of voltaic cell?




                Take a look at the equation you are using to figure out the emf. You are already treating the oxidation half reaction differently than the reduction half reaction because there is a negative sign in front of the anode reduction potential.



                $$E_textcell^circ = E_textcathode^circ - E_textanode^circ$$



                If you switch the anode and cathode half reaction, you would get the opposite sign for the emf. (Not that the reaction would go in that direction.)






                share|improve this answer









                $endgroup$

















                  2












                  $begingroup$

                  Take a look at the two half reactions:



                  $$
                  beginalign
                  ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
                  ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
                  endalign
                  $$



                  If there is an electron for grabs (like the ones in the wire of a voltaic cell), $ceAg+(aq)$ and $ceSn^2+(aq)$ are competing for it. Whichever half reaction has the higher (more positive) reduction potential will win. If the reduction potentials are equal, it is a draw and the reaction is at equilibrium. So we are taking the difference of the reduction potentials to see in which direction the reaction will go.




                  No sign flipping while figuring out the emf of voltaic cell?




                  Take a look at the equation you are using to figure out the emf. You are already treating the oxidation half reaction differently than the reduction half reaction because there is a negative sign in front of the anode reduction potential.



                  $$E_textcell^circ = E_textcathode^circ - E_textanode^circ$$



                  If you switch the anode and cathode half reaction, you would get the opposite sign for the emf. (Not that the reaction would go in that direction.)






                  share|improve this answer









                  $endgroup$















                    2












                    2








                    2





                    $begingroup$

                    Take a look at the two half reactions:



                    $$
                    beginalign
                    ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
                    ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
                    endalign
                    $$



                    If there is an electron for grabs (like the ones in the wire of a voltaic cell), $ceAg+(aq)$ and $ceSn^2+(aq)$ are competing for it. Whichever half reaction has the higher (more positive) reduction potential will win. If the reduction potentials are equal, it is a draw and the reaction is at equilibrium. So we are taking the difference of the reduction potentials to see in which direction the reaction will go.




                    No sign flipping while figuring out the emf of voltaic cell?




                    Take a look at the equation you are using to figure out the emf. You are already treating the oxidation half reaction differently than the reduction half reaction because there is a negative sign in front of the anode reduction potential.



                    $$E_textcell^circ = E_textcathode^circ - E_textanode^circ$$



                    If you switch the anode and cathode half reaction, you would get the opposite sign for the emf. (Not that the reaction would go in that direction.)






                    share|improve this answer









                    $endgroup$



                    Take a look at the two half reactions:



                    $$
                    beginalign
                    ceAg+(aq) + e- &→ Ag(s) &qquad E^circ &= pu0.80 V \
                    ceSn^2+(aq) + 2 e- &→ Sn(s) &qquad E^circ &= pu-0.14 V
                    endalign
                    $$



                    If there is an electron for grabs (like the ones in the wire of a voltaic cell), $ceAg+(aq)$ and $ceSn^2+(aq)$ are competing for it. Whichever half reaction has the higher (more positive) reduction potential will win. If the reduction potentials are equal, it is a draw and the reaction is at equilibrium. So we are taking the difference of the reduction potentials to see in which direction the reaction will go.




                    No sign flipping while figuring out the emf of voltaic cell?




                    Take a look at the equation you are using to figure out the emf. You are already treating the oxidation half reaction differently than the reduction half reaction because there is a negative sign in front of the anode reduction potential.



                    $$E_textcell^circ = E_textcathode^circ - E_textanode^circ$$



                    If you switch the anode and cathode half reaction, you would get the opposite sign for the emf. (Not that the reaction would go in that direction.)







                    share|improve this answer












                    share|improve this answer



                    share|improve this answer










                    answered Mar 30 at 13:52









                    Karsten TheisKarsten Theis

                    5,605745




                    5,605745





















                        2












                        $begingroup$


                        My book tells me to keep the E∘half-cells as they are written in the
                        tables and simply put them in




                        Your book is then one of the few books which teaches electrochemistry properly. The sign of the electrode reduction potential is invariant. If reflects the sign of the electrostatic charge of the electrode with respect to hydrogen electrode. I don;t know if you like history or not, long time ago in the 1950s-60s showing the electrostatic sign of a cell by means of a specially designed electroscope was a standard experiment in physics.



                        Imagine if I say H2O (l) --> H2O (g) at 100 oC



                        Does this mean reversing the reaction



                        H2O(g) --> H2O (l) will be at -100 oC?



                        You can see logical fallacy in reversing the sign of electrode potentials.



                        Yes, there was a lot of confusion in electrode signs for more than 100 years but now it has been sorted out.






                        share|improve this answer









                        $endgroup$

















                          2












                          $begingroup$


                          My book tells me to keep the E∘half-cells as they are written in the
                          tables and simply put them in




                          Your book is then one of the few books which teaches electrochemistry properly. The sign of the electrode reduction potential is invariant. If reflects the sign of the electrostatic charge of the electrode with respect to hydrogen electrode. I don;t know if you like history or not, long time ago in the 1950s-60s showing the electrostatic sign of a cell by means of a specially designed electroscope was a standard experiment in physics.



                          Imagine if I say H2O (l) --> H2O (g) at 100 oC



                          Does this mean reversing the reaction



                          H2O(g) --> H2O (l) will be at -100 oC?



                          You can see logical fallacy in reversing the sign of electrode potentials.



                          Yes, there was a lot of confusion in electrode signs for more than 100 years but now it has been sorted out.






                          share|improve this answer









                          $endgroup$















                            2












                            2








                            2





                            $begingroup$


                            My book tells me to keep the E∘half-cells as they are written in the
                            tables and simply put them in




                            Your book is then one of the few books which teaches electrochemistry properly. The sign of the electrode reduction potential is invariant. If reflects the sign of the electrostatic charge of the electrode with respect to hydrogen electrode. I don;t know if you like history or not, long time ago in the 1950s-60s showing the electrostatic sign of a cell by means of a specially designed electroscope was a standard experiment in physics.



                            Imagine if I say H2O (l) --> H2O (g) at 100 oC



                            Does this mean reversing the reaction



                            H2O(g) --> H2O (l) will be at -100 oC?



                            You can see logical fallacy in reversing the sign of electrode potentials.



                            Yes, there was a lot of confusion in electrode signs for more than 100 years but now it has been sorted out.






                            share|improve this answer









                            $endgroup$




                            My book tells me to keep the E∘half-cells as they are written in the
                            tables and simply put them in




                            Your book is then one of the few books which teaches electrochemistry properly. The sign of the electrode reduction potential is invariant. If reflects the sign of the electrostatic charge of the electrode with respect to hydrogen electrode. I don;t know if you like history or not, long time ago in the 1950s-60s showing the electrostatic sign of a cell by means of a specially designed electroscope was a standard experiment in physics.



                            Imagine if I say H2O (l) --> H2O (g) at 100 oC



                            Does this mean reversing the reaction



                            H2O(g) --> H2O (l) will be at -100 oC?



                            You can see logical fallacy in reversing the sign of electrode potentials.



                            Yes, there was a lot of confusion in electrode signs for more than 100 years but now it has been sorted out.







                            share|improve this answer












                            share|improve this answer



                            share|improve this answer










                            answered Mar 30 at 18:12









                            M. FarooqM. Farooq

                            2,260112




                            2,260112





















                                1












                                $begingroup$

                                The Nernst equation and electrochemical potentials relate to redox systems, not to reagents and products. The forward and reversed reactions are the same redox system.



                                Imagine you would want to make a galvanical cell with the same electrodes. Flipping the sign would grant you a Nobel price for inventing a perpetuum mobile.






                                share|improve this answer









                                $endgroup$

















                                  1












                                  $begingroup$

                                  The Nernst equation and electrochemical potentials relate to redox systems, not to reagents and products. The forward and reversed reactions are the same redox system.



                                  Imagine you would want to make a galvanical cell with the same electrodes. Flipping the sign would grant you a Nobel price for inventing a perpetuum mobile.






                                  share|improve this answer









                                  $endgroup$















                                    1












                                    1








                                    1





                                    $begingroup$

                                    The Nernst equation and electrochemical potentials relate to redox systems, not to reagents and products. The forward and reversed reactions are the same redox system.



                                    Imagine you would want to make a galvanical cell with the same electrodes. Flipping the sign would grant you a Nobel price for inventing a perpetuum mobile.






                                    share|improve this answer









                                    $endgroup$



                                    The Nernst equation and electrochemical potentials relate to redox systems, not to reagents and products. The forward and reversed reactions are the same redox system.



                                    Imagine you would want to make a galvanical cell with the same electrodes. Flipping the sign would grant you a Nobel price for inventing a perpetuum mobile.







                                    share|improve this answer












                                    share|improve this answer



                                    share|improve this answer










                                    answered Mar 30 at 13:00









                                    PoutnikPoutnik

                                    1,796313




                                    1,796313



























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