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JSOLVED PROBLEMS ON ELECTROCHEMISTRY (ii) For the electrochemical cell in which this reaction takes place which electrode is

negative electrode?
Example 1: Construct the cells in which the following reactions are taking place. Which of
the electrodes shall act as anode (negative electrode) and which one as cathode (positive Solution: (i) The half reactions are:
electrode)? 2Ag+ + 2e- --> 2Ag. Reduction
(a) Zn + CuSO4 = ZnSO4 + Cu (Cathode)
(b) Cu + 2AgNO3 = Cu(NO3)2 + 2 Ag EoAg+/Ag =0.80 volt (Reduction potential)
(c) Zn + H2SO4 = ZnSO4 + H2
(d) Fe + SnCl2 = FeCl2 + Sn Cd --> Cd2+ + 2e-, Oxidation
(Anode)
Solution: It should always be kept in mind that the metal which goes into solution in the EoCd+/Cd = -0.40 volt (Reduction potential)
form of its ions undergoes oxidation and thus acts as negative electrode (anode) and the or EoCd+/Cd2 = +0.40 volt
element which comes into the free state undergoes reduction and acts as positive electrode
(cathode): Eo = EoCd+/Cd2 + EoAg+/Ag = 0.40+0.80 = 1.20 volt

(a) In this case Zn is oxidized to Zn2+ and thus acts as anode (negative electrode) (ii) The negative electrode is always the electrode whose reduction potential has smaller
2+
while Cl is reduced to copper and thus acts as cathode (positive electrode). The cell can value or the electrode where oxidation occurs. Thus, Cd electrode is the negative electrode.
be represented
as Zn|ZnSO4||CuSO4|Cu
or Zn|Zn2+||Cu2+|Cu Example 3: Consider the cell, Zn|Zn2+(aq)(1.0M)||Cu2+(aq)(1.0M)|Cu. The standard
Anode (-) Cathode (+) electrode potentials are:
Cu2+ + 2e- --> Cu(aq) Eo = 0.350 volt
(b) In this case Cu is oxidized to Cu2+ and Ag+ is reduced to Ag. The cell can be 2+ -
Zn + 2e --> Zn(aq) Eo = -0.763 volt
represented as (i) Write down the cell reaction.
Cu|Cu(NO3)2||AgNO3|Ag (ii) Calculate the emf of the cell
or Cu|Cu2+||Ag+|Ag
Anode (-) Cathode (+) Solution: (i) Reduction potential of Zn is less than copper, hence Zn acts as anode and
copper as cathode.
(c) In this case Zn is oxidized to Zn2+ and H+ is reduced to H2. The cell can be
represented as At anode Zn --> Zn2+ + 2e- (Oxidation)
Zn|ZnSO4||H2SO4|Cu At cathode Cu + 2e- --> Cu
2+
(Reduction)
or Zn|Zn2+||2H+|H2(Pt) --------------------------------------------------------
Anode (-) Cathode (+) Cell reaction Zn + Cu2+ --> Zn2+ + Cu

(d) Here Fe is oxidized to Fe2+ and Sn2+ is reduced to Sn. The cell can be represented (ii) EoCell = EoZn/Zn2+ + EoCu2+/Cu
as = Oxi. Potential of zinc + Red. Potential of copper
Fe|FeCl2||SnCl2|Sn
or Fe|Fe2+||Sn2+|Sn EoZn/Zn2+ = -0.763 (Reduction potential)
Anode (-) Cathode (+) EoZn2+/Zn= +0.763 (Oxidation potential)
Example 2: Consider the reaction, 2Ag+ + Cd --> 2Ag + Cd2+. The standard electrode and EoCu2+/Cu = 0.350 (Reduction potential)
potentials for Ag+ --> Ag and Cd2+ --> Cd couples are 0.80 volt and -0.40 volt, respectively.
(i) What is the standard potential Eo for this reaction? So Ecello= 0.763+0.350 = 1.113 volt
Oxidation potential is EoM/Ma+ while reduction potential is represented as EoMa+/M. Writing two half reaction,
The value of EoZn/Zn2+ (oxidation potential of Zn) is +0.76 volt and the value of EoCu2+/Cu Fe --> Fe2+ + 2e- Oxidation EoFe/Fe2+ = 0.44 volt
(reduction potential of copper) is +0.34 volt. The electrode having lower value of reduction 2H++ 2e- --> H2 Reduction EoH+/H = 0.0 volt
potential acts as an anode while that having higher value of reduction potential acts as --------------------------------------
cathode. Adding, emf = 0.44 volt
Since emf is positive, the reaction shall occur.

Example 4: Write the electrode reactions and the net cell reactions for the following cells.
Which electrode would be the positive terminal in each cell? Example 6: The values of Eo of some of the reactions are given below:
(a) Zn|Zn2+||Br-, Br2|Pt I2 + 2e- --> 2I-; Eo = +0.54 volt
(b) Cr|Cr3+||I-, I2|Pt -
Cl2 + 2e --> 2Cl ;-
Eo = +1.36 volt
(c) Pt |H2, H+||Cu2+|Cu 3+ -
Fe + e --> Fe ; 2+
Eo = +0.76 volt
(d) Cd|Cd2+||Cl-, AgCl|Ag 4+ -
Ce + e --> Ce ; 3+
Eo = +1.60 volt
Solution: (a) Oxidation half reaction, Zn --> Zn2++2e- 4+ -
Sn + 2e --> Sn ; 2+
Eo = +0.15 volt
Reduction half reaction, Br2 + 2e- --> 2Br- On the basis of the above data, answer the following questions:
------------------------------------------------- (a) Whether Fe3+ oxidizes Ce3+ or not ?
Net cell reaction Zn + Br2 --> Zn2+ + 2Br- (b) Whether I2 displaces chlorine form KCl ?
Positive terminal-Cathode Pt (c) Whether the reaction between FeCl3 and SnCl2 occurs or not?

(b) Oxidation half reaction, [Cr --> Cr3+ + 3e-]× 2 Solution: (a) Chemical reaction, Fe3+ + Ce3+ --> Ce4+ + Fe2+
Reduction half reaction, [I2 + 2e- --> 2Ir-] × 3 Two half reactions,
---------------------------------------------------- Fe3+ + e --> Fe2+ Reduction Eo = 0.76 volt
Net cell reaction 2Cr + 3I2 --> 2Cr3+ + 6I- 3+ 4+
Ce --> Ce + e -
Oxidation Eoox = -1.60 volt
Positive terminal-Cathode Pt ---------------------------
Adding = -0.84 volt
(c) Oxidation half reaction, H2 --> 2H+ + 2e- Since, emf is negative the reaction does not occur, i.e., Fe3+ does not oxidise Ce3+.
Reduction half reaction, Cu2+ + 2e---> Cu
------------------------------------------------- (b) Chemical reaction I2 + 2KCl = 2Kl + Cl2
Net cell reaction H2 + Cu2+ --> Cu + 2H+ Half reactions
Positive terminal-Cathode Cu I2 + 2e- --> 2I- Reduction Eo = 0.54 volt
- -
2Cl --> Cl2 + 2e Oxidation Eoox = -1.36 volt
(d) Oxidation half reaction, Cd --> Cd2+ + 2e- ---------------------------
Reduction half reaction, [AgCl+e- --> Ag+Cl- ]×2 Adding = -0.82 volt
------------------------------------------------------ Since, emf is negative, the reaction does not occur, i.e., I2 does not displace Cl2 from KCl.
Net cell reaction Cd+2AgCl --> Cd2++2Ag+2Cl-
Positive terminal-Cathode Ag (c) Chemical reaction SnCl2 + 2FeCl3 --> SnCl4 + 2FeCl2
Half reactions
Fe3+ + e Fe2+ Reduction Eo = 0.76 volt
Example 5: Will Fe be oxidised to Fe2+ by reaction with 1.0 M HCl? Eo for Fe/Fe2+ = +0.44 Ce Sn + 2e Oxidation Eo = -0.15 volt
2+ 4+ -

volt. -------------------------
Adding = +0.61 volt
Solution: The reaction will occur if FE is oxidized to Fe2+. Since, emf is positive, the reaction will occur.
Fe + 2HCl --> FeCl2 + H2
Example 7: Calculate the electrode potential at a copper electrode dipped in a 0.1 M Example 10: The emf(E°) of the following cells are:
solution of copper sulphate at 25o C. The standard electrode potential of Cu2+/Cu system is Ag|Ag|(1 M)||Cu2+(1 M)|Cu; E° = -0.46 volt
0.34 volt at 298 K. Zn|Zn2(1 M)||Cu2|(1 M)|Cu; E° = +1.10 volt
Calculate the emf of the cell:
Solution: We know that Ered = Eored + 0.0591/n log10[ion] Zn|Zn2+(1 M)||Ag+(1 M)|Ag
Putting the values of Eored =0.34 V, n = 2 and [Cu2+]= 0.1 M
Eored = 0.34+0.0591/2 log10[0.1] Solution: Zn|Zn2+(1 M)||Ag+(1 M)|Ag
= 0.34 + 0.02955 × (-1) Ecell = Eox(Zn/Zn2+) + Ered (Ag+/Ag)
= 0.34 - 0.02955 = 0.31045 volt
With the help of the following two cells, the above equation can be obtained.
Ag|Ag+(1 M)||Cu2+(1 M)|Cu, E° = -0.46 volt
Example 8: What is the single electrode potential of a half-cell foe zinc electrode dipping or Cu|Cu2+(1 M)||Ag+(1 M)|Ag, E° will be +0.46 volt
in 0.01 M ZnSO4 solution at 25o C? The standard electrode potential of Zn/Zn2+ system is
0.763 volt at 25o C. or +0.46 = Eox(cwcu2+) + Ered (Ag+/Ag) .... (i)
Zn|Zn2+(1 M)||Cu2+1|Cu, E° = +1.10 volt
Solution: We know that Eox = Eored - 0.0591/n log10[ion] + 1.10 = Eox(Zn/Zn+) + Ered(Cu2+/Cu) ....... (ii)
Putting the value of Eoox=0.763 V,n=2 and Adding Eqs. (i) and (ii),
2+
[Zn ]=0.01 M + 1.56 = Eox(Cu/Cu2+) + Ered(Ag+/Ag) + Eox(Zn/Zn2+) + Ered(Cu2+/Cu)
Eoox = 0.763-0.0591/2 log_10 [0.01] = 0.763 - 0.02955 × (-2) Since Eox(Cu/Cu2+) - Ered(Cu2+/Cu)
= (0.763 + 0.0591) volt = 0.8221 volt
Example 9: The standard oxidation potential of zinc is 0.76 volt and of silver is -0.80 volt. So +1.56 = Em(Zn/Zn+) + Ered(Ag+/Ag)
Calculate the emf of the cell at 250C. Thus, the emf of the following cell is
Zn|Zn(NO3)2||AgNO3|Ag Zn|Zn2+(1 M)||Ag+(1 M)|Ag is +1.56 volt.
0.25 M 0.1 M

Solution: The cell reaction is Zn + 2 Ag+ --> 2Ag + Zn2+ Example 11: Calculate the e.m.f of the cell. Mg(s)|Mg2+(0.2M)||Ag+(1×10-3)|Ag
Eoox of Zn = 0.76 volt EoAg+/Ag = +0.8 volt, EoMg2+/Mg = -2.37 volt
Eoox of Ag = 0.80 volt What will be the effect on e.m.f. if concentration of Mg2+ ion is decreased to 0.1 M?
Eocell = Eoox of Zn + of Ag = 0.76 + 0.80
= 1.56 volt Solution: Eocell = EoCathode - Eoanode = 0.80-(-2.37) = 3.17 volt
= 1.56 - 0.0591/2×1.3979 Cell reaction Mg + 2Ag+ --> 2Ag + Mg2+
= (1.56-0.0413) volt Ecell = Ecello - 0.0591/n log(Mg2+)/[Ag+]2
= 1.5187 volt = 3.17 -0.0591/2 log 0.2/[1× 10-3 ]2
= 3.17 - 0.1566 = 3.0134 volt
Alternative method: First of all, the single electrode potentials of both the electrodes are when Mg2+ = 0.1 M
determined on the basis of given concentrations. Ecell = Eocell - 0.0591/n log(0.1)/[1 x 10-3]2
Eox(Zinc) = Eoox -0.0591/2 log 0.25 = (3.17 - 0.1477) volt
= 0.76 + 0.0177 = 0.7777 volt = 3.0223 volt
Ered(Silver) = Eored -0.0591/2 log 0.1
= 0.80 + 0.0591 = 0.7409 volt
Ecell = Eox(Zinc) + Ered(Silver) Example 12: To find the standard potential of M3+/M electrode, the following cell is
constituted: Pt|M|M3+(0.0018 mol-1L)||Ag+(0.01 mol-1L)|Ag. The emf of this cell is found to
be 0.42 volt. Calculate the standard potential of the half reaction M3+ + 3e- M3+. = 0.80 O2(g) + 4 H+(aq) + 4 e- 2
volt. reduction: Eored. = + 1.229 V
H2O(l)
Solution: The cell reaction is M + 3Ag+ ---> 3Ag + M3+
Applying Nernst equation, O2(g) + 4 H+(aq) + 4 Br-(aq) 2
overall: Eocell = + 0.152 V
Ecell = Ecello - 0.0591/n log(Mg2+)/[Ag+]3 H2O(l) + 2 Br2(l)
0.42 = Ecello - 0.0591/n log (0.0018)/(0.01)3 = Ecello - 0.064
Ecello =(0.042+0.064)= 0.484 volt
Eocell = Eocathode - Eoanode
or Eoanode = Eocathode - Eocell Determine the new cell potential resulting from the changed conditions.
= (0.80-0.484) = 0.32 volt o Calculate the value for the reaction quotient, Q. (Note: We calculate Q
using molar concentrations for solutions and pressures for gases. Water
Example 13: Find the standard cell potential for an electrochemical cell with the following and bromine are both liquids, therefore they are not included in the
cell reaction. calculation of Q.)
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Write the half-reactions for each process.
Zn(s) Zn2+(aq) + 2 e-
Cu (aq) + 2 e-
2+
Cu(s)
Look up the standard potentials for the redcution half-reaction.
Eoreduction of Cu2+ = + 0.339 V
Look up the standard reduction potential for the reverse of the oxidation reaction
and change the sign.
Eoreduction of Zn2+ = - 0.762 V o Calculate the number of moles of electrons transferred in the balanced
o
E oxidation of Zn = - ( - 0.762 V) = + 0.762 V equation, n.
Add the cell potentials together to get the overall standard cell potential. n = 4 moles of electrons
o Substitute values into the Nernst equation and solve for the non-standard
Eoox. = - Eored. = - (- 0.762 V) = +
oxidation: Zn(s) Zn2+(aq) + 2 e- cell potential, Ecell.
0.762 V
Ecell = + 0.152 V - (0.0257/4) ln(1.02 x 106)
reduction: Cu2+(aq) + 2 e- Cu(s) Eored. = + 0.339 V Ecell = 0.063 V

Zn(s) + Cu2+(aq) Zn2+(aq) +


overall: Eocell = + 1.101 V
Cu(s) Example 15: A 40.0 amp current flowed through molten iron(III) chloride for 10.0 hours
(36,000 s). Determine the mass of iron and the volume of chlorine gas (measured at 25oC
and 1 atm) that is produced during this time.
Example 14: Predict the cell potential for the following reaction when the pressure of the
oxygen gas is 2.50 atm, the hydrogen ion concentration is 0.10 M, and the bromide ion Write the half-reactions that take place at the anode and at the cathode.
concentration is 0.25 M. anode (oxidation): 2 Cl- Cl2(g) + 2 e-
O2(g) + 4 H+(aq) + 4 Br-(aq) 2 H2O(l) + 2 Br2(l) cathode (reduction) Fe + 3 e-
3+
Fe(s)
Calculate the number of moles of electrons.
Calculate the standard cell potential for the reaction, Eocell, using the tabled values:
Eoox. = - Eored. = - (+ 1.077 V)
oxidation: 4 Br-(aq) 2 Br2(l) + 4 e-
= - 1.077 V
Calculate the time using the current and the coulombs of charge.
Calculate the moles of iron and of chlorine produced using the number of moles of
electrons calculated and the stoichiometries from the balanced half-reactions.
According to the equations, three moles of electrons produce one mole of iron and
2 moles of electrons produce 1 mole of chlorine gas.
Example 17: What current is required to produce 400.0 L of hydrogen gas, measured at
STP, from the electrolysis of water in 1 hour (3600 s)?

Calculate the number of moles of H2. (Remember, at STP, 1 mole of any gas
occupies 22.4 L.)
Calculate the mass of iron using the molar mass and calculate the volume of
chlorine gas using the ideal gas law (PV = nRT).

Write the equation for the half-reaction that takes place.


Hydrogen is produced during the reduction of water at the cathode. The equation
for this half-reaction is:
4 e- + 4 H2O(l) 2 H2(g) + 4 OH-(aq)
Calculate the number of moles of electrons. According to the stoichiometry of the
equation, 4 mole of e- are required to produce 2 moles of hydrogen gas, or 2 moles
of e-'s for every one mole of hydrogen gas.
Example 16: How long must a 20.0 amp current flow through a solution of ZnSO4 in
order to produce 25.00 g of Zn metal.
Convert the moles of electrons into coulombs of charge.
Convert the mass of Zn produced into moles using the molar mass of Zn.

Write the half-reaction for the production of Zn at the cathode.


Zn2+(aq) + 2 e- Zn(s)
-
Calculate the moles of e required to produce the moles of Zn using the Calculate the current required.
stoichiometry of the balanced half-reaction. According to the equation 2 moles of
electrons will produce one mole of zinc.

Convert the moles of electrons into coulombs of charge using Faraday's constant. Example 18: Calculate the volume of H2 gas at 25oC and 1.00 atm that will collect at the
cathode when an aqueous solution of Na2SO4 is electrolyzed for 2.00 hours with a 10.0-amp
current.
this result in a conspicuous location, and go back to the original statement of the question,
Solution: We start by calculating the amount of electrical charge that passes through the to see what else can be done.
solution. The problem tells us the mass of chromium deposited at the cathode. By now it should be
obvious that we need to transform this information into the number of moles of chromium
metal generated.

We then calculate the number of moles of electrons that carry this charge.

We now know the number of moles of chromium metal produced and the number of molus
of electrons it took to produce this metal. We might therefore look at the relationship
between the moles of electrons consumed in this reaction and the moles of chromium
The balanced equation for the reaction that produces H2 gas at the cathode indicates that produced.
we get a mole of H2 gas for every two moles of electrons.
Cathode (-): 2 H2O + 2 e- H2 + 2 OH-
We therefore get one mole of H2 gas at the cathode for every two moles of electrons that
flow through the cell. Three moles of electrons are consumed for every mole of chromium metal produced. The
only way to explain this is to assume that the net reaction at the cathode involves reduction
of Cr3+ ions to chromium metal.
Cathode (-): Cr3+ + 3 e- Cr
We now have the information we need to calculate the volume of the gas produced in this Thus, the oxidation number of chromium in the unknown salt must be +3.
reaction.

Example 20: Calculate the EMF of the cell Zn(s) | Zn2+ (0.024 M) || Zn2+ (2.4 M) | Zn(s)

Solution
Example 19: Determine the oxidation number of the chromium in an unknown salt if
Zn2+ (2.4 M) + 2 e = Zn Reduction
electrolysis of a molten sample of this salt for 1.50 hours with a 10.0-amp current deposits
Zn = Zn2+ (0.024 M) + 2 e Oxidation
9.71 grams of chromium metal at the cathode.
--------------------------------------------
Zn2+ (2.4 M) = Zn2+ (0.024 M), DE° = 0.00 - - Net reaction
Solution We start, as before, by calculating the number of moles of electrons that passed
through the cell during electrolysis.
Using the Nernst equation:
0.0592 (0.024)
DE = 0.00 - ------- log --------
2 (2.4)

= (-0.296)(-2.0) = 0.0592 V

Since we don't know the balanced equation for the reaction at the cathode in this cell, it
Discussion
Understandably, the Zn2+ ions try to move from the concentrated half cell to a dilute
doesn't seem obvious how we are going to use this information. We therefore write down
solution. That driving force gives rise to 0.0592 V. From here, you can also calculate the
energy of dilution. Example 23: From the standard cell potentials, calculate the solubility product for the
If you write the equation in the reverse direction, following reaction: AgCl = Ag+ + Cl-
Zn2+ (0.024 M) = Zn2+ (2.4 M),
its voltage will be -0.0592 V. At equilibrium concentrations in the two half cells will have to Solution
be equal, in which case the voltage will be zero. There are Ag+ and AgCl involved in the reaction, and from the table of standard reduction
potentials, you will find:
AgCl + e = Ag + Cl-, E° = 0.2223 V - - - -(1)
Example 21: Show that the voltage of an electric cell is unaffected by multiplying the Since this equation does not contain the species Ag+, you need,
reaction equation by a positive number. Ag+ + e = Ag, E° = 0.799 V - - - - - - (2)
Subtracting (2) from (1) leads to,
Solution Assume that you have the cell Mg | Mg2+ || Ag+ | Ag and the reaction is: Mg + AgCl = Ag+ + Cl- . . . DE° = - 0.577
2 Ag+ = Mg2+ + 2 Ag. Using the Nernst equation Let Ksp be the solubility product, and employ the Nernst equation,
0.0592 [Mg2+] log Ksp = (-0.577) / (0.0592) = -9.75
DE = DE° - ------ log -------- Ksp = 10-9.75 = 1.8x10-10
2 [Ag+]2 This is the value that you have been using in past tutorials. Now, you know that Ksp is not
If you multiply the equation of reaction by 2, you will have always measured from its solubility.
2 Mg + 4 Ag+ = 2 Mg2+ + 4 Ag

Note that there are 4 electrons involved in this equation, and n = 4 in the Nernst equation: Example 24: Calculate the thickness of chromium plating deposited in 2> mm. at a
0.0592 [Mg2+]2 current density of 180 amp. per square foot and a current efficiency of 14 per cent.
DE = DE° - ------ log --------
4 [Ag+]4 Solution: The number of coulombs flowing is 180 X 2.5 X 60 27,000 per square
which can be simplified as foot. The solution is of CrO3 , m which chromium has a valence of 6. The weight
of Or theoretically deposited is therefore:
0.0592 [Mg2+]
DE = DE° - ------ log --------
2 [Ag+]2
Thus, the cell potential DE is not affected.
The actual deposit is 0.14 X 2.42 = 0.34 g. per square foot = or 0.00037 g.
per square centimeter.
Example 22: The standard cell potential dE° for the reaction Fe + Zn2+ = Zn + Fe2+ is -
0.353 V. If a piece of iron is placed in a 1 M Zn2+ solution, what is the equilibrium The density of Cr is 7.1 g. per cubic centimeter.
concentration of Fe2+?
The thickness is therefore = 0.000052 cm. = 0.0000205 in.
Solution The equilibrium constant K may be calculated using
K = 10(n DE°)/0.0592
= 10-11.93
= 1.2x10-12
= [Fe2+]/[Zn2+].
2+
Since [Zn ] = 1 M, it is evident that
[Fe2+] = 1.2E-12 M.