Problems based on Nernst Equation:
1) Determine the Nernst potential of the following system. Also Identify the electrode system as
Oxidation or Reduction system.(Data Given: E°Zn 2+ = - 0.76 V)
Zn (s)/ Zn2+ (0.1 M) (aq) at 25°C
2) Determine the Electrode potential of the following system. Also Identify the electrode system as
Oxidation or Reduction system.(Data Given: E°Cu 2+ = 0.34 V)
Cu2+ (0.1 M) (aq) /Cu (s) at 25°C
3 )Determine the Concentration of the electrolyte in the following system.(Data Given: E° Zn 2+ = - 0.76 V &
EZn = - 0.79 V)
Zn (s)/ Zn2+ (x M) (aq) at 25°C
4) Determine the electrode potential of a univalent reduction favorable electrode which is dipped in a
0.1 M electrolyte solution at 25°C. .(Data Given: E°X+ = 0.8 V)
To solve such problems always use the Nernst equation in its general for i.e.
E= E° - 2.303 RT/nF x Log[P]/[R]
Where E is Electrode potential (Neither Reduction potential nor Oxidation Potential. It takes the form of
Reduction Potential (E) or Oxidation potential Eox only when [P] and [R] are defined.
Note: Standard form of expressing Reduction potential is (E) and Oxidation potential as E ox
Similarly E° is Standard Electrode potential (Neither Standard Reduction potential nor Standard
Oxidation Potential. It takes the form of Standard Reduction Potential (E°) or Standard Oxidation
potential E° ox only when [P] and [R] are defined.
To define [P] and [R] you must first decide whether you are finding Reduction potential or Oxidation
Potential and accordingly write the relevant reaction i.e. Reduction and oxidation reaction respectively.
In numerical if you are asked to find Electrode potential, then you can calculate either Reduction
potential or Oxidation Potential irrespective of the representation given.
1) Determine the Nernst potential of the following system. Also Identify the electrode system as
Oxidation or Reduction system.(Data Given: E°Zn 2+ = - 0.76 V)
Zn (s)/ Zn2+ (0.1 M) (aq) at 25°C
2) Determine the Electrode potential of the following system. Also Identify the electrode system as
Oxidation or Reduction system.(Data Given: E°Cu 2+ = 0.34 V)
Cu2+ (0.1 M) (aq) /Cu (s) at 25°C
3 )Determine the Concentration of the electrolyte in the following system.(Data Given: E° Zn 2+ = - 0.76 V &
EZn = - 0.79 V)
Zn (s)/ Zn2+ (x M) (aq) at 25°C
4) Determine the electrode potential of a univalent reduction favorable electrode which is dipped in a
0.1 M electrolyte solution at 25°C. .(Data Given: E°X+ = 0.8 V)
Solution 1) Question is having two components i.e. Determining Electrode potential (E) which means
Nernst potential and to identify it as Oxidation or Reduction system.
To identify it as oxidation or reduction system you have to look at the representation. In this
case the representation given is Zn (s)/ Zn2+ (0.1 M) (aq) which is a anodic representation ( refer lecture 2
notes)
Hence it is a Oxidation system.
To determine the Nernst Potential use the Nernst equation and decide whether you want to
solve for Reduction of Oxidation Electrode Potential.
Case 1. To determine the Reduction Electrode potential write the reduction reaction
i.e. Zn2+ + 2e Zn (we know it is bivalent from the data given i.e. : E°Zn 2+ = - 0.76 V)
Hence [P] is [Zn] and [R] is [ Zn2+] so Ezn = ? E°Zn 2+ = - 0.76 V ; also [Zn] being solid
concentration is taken as unity and [ Zn2+] = 0.1 M
Now substitute in E= E° - 2.303 RT/nF x Log[P]/[R]
E= E° - 0.059/n x Log[P]/[R] at 25°C
Ezn = -0.76 - 0.059log [Zn]
2 [ Zn2+]
Ezn = -0.76 - 0.059log 1
2 0.1
Ezn = - 0.76 + 0.295(log 0.1)
Ezn = - 0.7895 V
Case 2. To determine the Oxidation Electrode potential write the reduction reaction i.e.
Zn Zn2+ + 2e (we know it is bivalent from the data given i.e. : E°Zn 2+ = - 0.76 V)
Hence [P] is [ Zn2+] and [R] is [Zn] so Ezn(ox) = ? E°Zn 2+(ox) = + 0.76 V ; also [Zn] being solid
concentration is taken as unity and [ Zn2+] = 0.1 M
Now substitute in E= E° - 2.303 RT/nF x Log[P]/[R]
E= E° - 0.059/n x Log[P]/[R] at 25°C
Ezn(ox) = 0.76 - 0.059log [ Zn2+]
2 [Zn]
Ezn(ox)= 0.76 - 0.059log 0.1
2 1
Ezn(ox) = 0.76 - 0.295(log 0.1)
Ezn(ox)= 0.7895 V
Solution 1) Question is having two components i.e. Determining Electrode potential (E) which means
Nernst potential and to identify it as Oxidation or Reduction system.
To identify it as oxidation or reduction system you have to look at the representation. In
this case the representation given is Cu2+ (0.1 M) (aq) /Cu (s) (aq) which is a cathodic
representation ( refer lecture 2 notes)
Hence it is a Reduction system.
To determine the Nernst Potential use the Nernst equation and decide whether you
want to solve for Reduction of Oxidation Electrode Potential.
Take any case as shown in solution 1 and solve.
Case 1. To determine the Reduction Electrode potential write the reduction reaction i.e.
2+
Cu + 2e Cu (we know it is bivalent from the data given i.e. : E°Cu 2+ = + 0.34 V)
Hence [P] is [Cu] and [R] is [ Cu2+] so ECu = ? E°Cu 2+ = - 0.76 V ; also [Cu] being solid
concentration is taken as unity and [ Cu2+] = 0.1 M
Now substitute in E= E° - 2.303 RT/nF x Log[P]/[R]
E= E° - 0.059/n x Log[P]/[R] at 25°C
Ezn = 0.34 - 0.059log [Cu]
2 [ Cu2+]
Ezn = 0.34 - 0.059log 1
2 0.1
Ezn = 0.34 + 0.295(log 0.1)
Ezn = 0.3105 V
Important note: You can use these points for validating your answer.
1) If the standard reduction potential of any element is negative than its standard
Oxidation potential shall be positive and vice versa.
2) If the given system is oxidation favorable system, and the concentration of
electrolyte is less than 1 M than resultant magnitude of E shall be greater than E°
and if it is greater than 1M than resultant magnitude of E shall be less than E°
3) If the given system is reduction favorable system, and the concentration of
electrolyte is less than 1 M than resultant magnitude of E shall be lessr than E° and if
it is greater than 1M than resultant magnitude of E shall be more than E°
Solution 3: .(Data Given: E°Zn 2+ = - 0.76 V & EZn = - 0.79 V) : Zn (s)/ Zn2+ (x M) (aq) at 25°C
[ Zn2+] = ? M
Zn2+ + 2e Zn
Ezn = -0.76 - 0.059log [Zn]
2 [ Zn2+]
-0.79 = -0.76 - 0.059log [Zn]
2 [ Zn2+]
Ezn = -0.76 - 0.059log 1
2 x
Ezn = - 0.76 + 0.295(log x)
x = 0.09 M
Solution 4: Determine the electrode potential of a univalent reduction favorable electrode
which is dipped in a 0.1 M electrolyte solution at 25°C. .(Data Given: E°X+ = 0.8 V)
Univalent implies n= 1 [X+] = 0.1 M
+
X +e X
Ex = E°x - 0.059log [x]
2 [ x+]
Ex = 0.8 - 0.059log 1
1 0.1
Ex = 0.8 + 0.059log 0.1
1
Ex = 0.8 -0.059
Ex = 0.741 V
Numericals related to Determination of Electrochemical cell potential (E cell)
1) Determine the Standard cell potential for the electrochemical cell formed by using
Zn and Cu electrodes at 25 °C. Also write its representation and reactions involved.
(Data Given E°Zn2+ = -0.76 V & E°Cu2+ = 0.34 V
2) Formulate an Electrochemical cell using Zn and Mg electrodes which are dipped in
their respective electrolyte concentration of 0.01 M and 0.1 M respectively. Also
determine its Cell potential and write the reactions involved. (Data Given E° Zn2+ = -
0.76 V & E°Mg2+ = - 2.37 V)
3) Formulate an Electrochemical cell using Mg and Al electrodes which are dipped in their
respective electrolyte concentration of 0.01 M and 0.1 M respectively. Also determine its
Cell potential and write the reactions involved. (Data Given E°Mg2+ = -2.37 V & E°Al3+ = - 1.66
V)
4) Determine the Electrochemical Cell potential of the following cell: Sn(s)/Sn 2+ (aq)
(0.001M) // Ag + (aq) (1M) /Ag(s) (Data Given E°Sn2+ = - 0.14 V & E°Ag+ = 0.8 V)
5) Formulate a concentration cell using Silver electrodes with electrolyte concentration of
0.05 M and 0. 5 M and determine its Cell Potential at 25 °C (Data Given E° Ag+ = 0.8 V)
6) Determine the cell potential of the following cell at 25 °C : Sn(s)/Sn2+ (aq)(0.001M) // Sn2+
(aq)(0.01M) /Sn(s) (Data Given E°Sn2+ = - 0.14 V)
7) You are given the following elements Zn, Sn, Ni and Mg and their respective salt solutions
in concentrations 0.1 M, 1M, 0.01 M & 0.001 M. Using the materials formulate a Voltaic
and Concentration cell that shall yield the highest cell potential. (Data Given E° Sn2+ = - 0.14
V, E°Mg2+ = -2.37 V, E°Zn2+ = -0.76 V & E°Ni2+ = -0.23 V )
Points to remember while solving such numerical:
1) We have two types of Electrochemical cells viz. Voltaic/Galvanic cell and Concentration cell . (refer
lecture notes no. 5)
2) Ecell implies Electrochemical cell potential, E°cell implies standard Electrochemical cell potential
( when both half cells are working under standard conditions)and Ecell (conc) implies Concentration cell
Potential.
3) Equations to be used : Ecell = Ecathode -Eanode where Ecathode & Eanode are reduction potential values.
4) E°cell = E°cathode -E°anode where E°cathode & E°anode are standard reduction potential values.
5) Ecell = E°cell - 2.303 RT/nF x Log[P]/[R] where [P] and [R] are to be obtained after writing the net
cell reaction. This equation is obtained from
Ecell = Ecathode -Eanode and E°cell is obtained from 4 above.
6) Ecell (conc) =2.303RT/nF x Log[higherConc]
[LowerConc]
Solution 1: First we have to identify which element will act as anode and cathode by examining
their E° values. The more negative value will act as Oxidation half cell in relation to the more
positive value. In this case we have
E°Zn2+ = -0.76 V & E°Cu2+ = 0.34 V, so Zn will form the anode and Cu will form the cathode.
So three things are asked 1) Representation 2) Reactions 3) E°cell ?
Representation: Zn//Zn2+ (aq) (1M) //Cu2+ (aq) (1M)/Cu we have chosen 1M since we
are finding Standard cell potential (refer lecture notes 1,2,3)
Reactions: Zn Zn2+ + 2e
Cu2+ + 2e Cu
Net cell reaction: Zn + Cu2+ Zn2+ + Cu
Calculation of E°cell : E°cell = E°cathode -E°anode
= 0.34 – (-0.76)
= 1.1 V
Solution 2 : Remember the term ‘Formulate’ implies you have to form the cell meaning write its
representation.
Elements given are E°Zn2+ = -0.76 V & E°Mg2+ = - 2.37 V, so from the values we know that
Mg will act as anode half cell and Zinc will function as cathode half cell.
Representation: Mg//Mg2+ (aq) (0.1M) //Zn2+ (aq) (0.01M)/Zn
Reactions: Mg Mg2+ + 2e
Zn2+ + 2e Zn
Net cell reaction: Mg + Zn2+ Mg2+ + Zn
Calculation of Ecell: Ecell = E°cell – 0.059/n x Log[P]/[R] at 25°C
E°cell = E°cathode -E°anode
= -0.76 –(-2.37)
= 1.61 V
Ecell = 1.61 – 0.059/2 x Log[Mg2+][ Zn ]/[ Zn2+][ Mg]
Ecell = 1.61 - 0.059log 0.1
2 0.01
= 1.58 v
Solution 3: from these values E°Mg2+ = -2.37 V & E°Al3+ = - 1.66 V we know that Mg will act as anode half
cell and Al will act as cathode half cell.
Representation: Mg//Mg2+ (aq) (0.01M) //Al3+ (aq) (0.1M)/Al
Mg Mg2+ + 2e x3
Al3+ + 3e Al x2
Net cell reaction: 3Mg + 2 Al3+ 3Mg2+ + 2 Al n= 6
Calculation of Ecell: Ecell = E°cell – 0.059/n x Log[P]/[R] at 25°C
E°cell = E°cathode -E°anode
= -1.66 –(-2.37)
= 0.71 V
Ecell = 0.71– 0.059/6 x Log[Mg2+]3[ Al ]2/[ Al3+]2[ Mg]3
Ecell = 0.71 - 0.059log ( 0.01)3
6 ( 0.1)2
= 0.71 + 0.059 x 4/6
= 0.749 v
Solution 4: : from these values E°Sn2+ = - 0.14 V & E°Ag+ = 0.8 V we know that Sn will act as anode half cell
and Ag will act as cathode half cell.
Representation: : Sn(s)/Sn2+ (aq)(0.001M) // Ag + (aq) (1M) /Ag(s)
Sn Sn2+ + 2e
Ag+ + e Ag x2
Net cell reaction: Sn + 2 Ag+ Sn2+ + 2Ag n= 2
Calculation of Ecell: Ecell = E°cell – 0.059/n x Log[P]/[R] at 25°C
E°cell = E°cathode -E°anode
= 0.8 –(-0.14)
= 0.94 V
Ecell = 0.94 – 0.059/2 x Log[Sn2+][ Ag]2/[ Ag+]2[ Sn]
Ecell = 0.94 - 0.059log ( 0.001)
2 ( 1)2
= 1.028 v
Solution 5: Formulate a concentration cell using Silver electrodes with electrolyte
concentration of 0.05 M and 0. 5 M and determine its Cell Potential at 25 °C (Data Given
E°Ag+ = 0.8 V)
Since both electrodes are same it is a concentration cell.
Ag(s)/ Ag + (aq) (0.05M)//Ag + (aq) (0.5M) /Ag(s) remember
lesser concentration should be represented in anodic side as anodic half cell is oxidation half cell.
Ecell (conc) =0.059/n x Log[higherConc] at 25°C
[LowerConc]
= 0.059log 0.5
1 0.05
= 0.059 V
Solution 6: Sn(s)/Sn2+ (aq)(0.001M) // Sn2+ (aq)(0.01M) /Sn(s)
Ecell (conc) =0.059/n x Log[higherConc] at 25°C
[LowerConc]
= 0.059 log 0.01
2 0.001
= 0.0259 V
Solution 7 : To solve this type of problem first arrange the E° values in increasing positive
values so we have.
E°Mg2+ = -2.37 V,
E°Zn2+ = -0.76 V
E°Ni2+ = -0.23 V
E°Sn2+ = - 0.14 V
For Voltaic type cell we choose the two elements which are the end limits i.e.
Mg will act as anode and Tin as cathode and they shall give us the maximum
E°cell value.
Than we know that we can increase the E°cell value by choosing the
concentration values appropriately i.e. the least concentration in anodic half
cell and highest concentration in cathodic half cell.
i.e. 0.001 M and 1M
hence we have
Mg//Mg2+ (aq) (0.001M) //Sn2+ (aq) (1M)/Sn
Mg Mg2+ + 2e
Sn2+ + 2e Sn
Mg + Sn2+ Mg2+ + Sn
Ecell = E°cell – 0.059/n x Log[P]/[R] at 25°C
E°cell = E°cathode -E°anode
= -0.14 –(-2.37)
= 2.23 V
Ecell = 2.23 – 0.059/2 x Log[Mg2+][ Sn]/[ Sn2+][ Mg]
Ecell = 2.23 - 0.059log ( 0.001)
2 ( 1)
= 2.3185v
Now for concentration cell remember only the n value will make a difference,
since in the given elements for all n=2 any element can be taken and a
concentration cell can be formed. The concentration shall again be 0.001 M and
1M
Sn(s)/Sn2+ (aq)(0.001M) // Sn2+ (aq)(1M) /Sn(s)
Ecell (conc) =0.059/n x Log[higherConc] at 25°C
[LowerConc]
= 0.059 log 1
2 0.001
= 0.0885 V
