Compiled by Dr. G. V. S.

Nageswara Rao, Assistant Professor, MMED, NITW

PROBLEM SET - 1
(Galvanic Cells)

1) The standard free energy of formation of MnO in the temperature range 298 to 1500K is
given as ∆G 0 = −91,950 + 17.4T calories, and the standard free energy of formation of
H2O in the temperature range 298 to 2500K is given as ∆G 0 = −58,900 + 13.1T calories.
a) Calculate the H2/H2O ratio in equilibrium with pure Mn and MnO at 1400K.
b) The reaction Mn + H2O = MnO + H2 is set up in a galvanic cell. Calculate the
standard EMF of the cell, the maximum work obtainable from this cell, and the heat
transfer between the cell and its constant temperature heat reservoir when it is
operated reversibly.
c) Calculate the EMF of the cell when the ratio of pressures of H2 and H2O is maintained
at 1000/1.
d) Manganese is alloyed with a metal X in the solid state. The composition of the alloy is
50 atom percent. The partial molar enthalpy of mixing of Mn in this alloy is −1150
calories. If the solution behaves regularly and the alloy is placed in the galvanic cell in
place of the pure manganese, calculate the EMF of the cell when pH 2 pH 2O = 1000.
e) If the MnO is dissolved in an oxide solution and a new EMF measurement is made for
any of the above cells, it is found that EMF has become more positive by 0.05 volt.
Calculate the activity of MnO in the oxide solution.

SOLUTION:

a) Given Mn( s) + 12 O2 ( g ) = MnO ( s ) , ∆G 0 = −91,950 + 17.4T calories, and

H 2 ( g ) + 12 O2 ( g ) = H 2O( g ) , ∆G 0 = −58,900 + 13.1T calories.

Now, for the reaction:

Mn( s ) + H 2O ( g ) = MnO( s) + H 2 ( g ) , ∆G 0 = −33,050 + 4.3T calories.
0
pH 2
∆G1400 = −27,030 calories , but ∆G 0 = − RT ln K , and K = so
pH 2O
0
− ∆G1400 27,030
ln K = = = 9.7167
1.987 x 1400 1.987 x 1400
 pH 2  pH 2
ln  = 9.7167 ⇒ = e9.7167 = 1.66 x 10 4
 
pH 2O  pH 2 O


∆G 0 27,030
b) As ∆G 0 = −nFE 0 , the EMF of the cell is given by E 0 = − =
nF 2 x 23,050
Therefore E0 = 0.5863 volt
′ = −∆G 0 = 27,030 calories
The maximum work obtainable from this cell = wmax
 − ∂ (∆G ) 
The heat transferred = q = T∆S 0 = T   = 1400 x (−4.3) = −6020 calories.
 ∂T  P
Thus 6020 calories of heat flow from the cell into the constant-temperature heat
reservoir per mole of reaction when the standard cell is operating reversibly.

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

RT  aMnO . pH 2 
c) For a cell, E = E 0 − ln
nF  aMn . pH 2O 
But, aMn = aMnO = 1 and pH 2 pH 2O = 1000
4.575 x 1400
E = 0.5863 − log(1000 ) = 0.1695 volt
2 x 23,050

d) In the regular system Mn-X,

mix Xs
∆H Mn = GMn = RT ln γ Mn = −1150 calories
1150
log γ Mn = − = −0.18 ⇒ γ Mn = 0.662
4.575 x 1400

Given NMn = 0.5

Therefore, aMn = γ Mn .N Mn = 0.662 x 0.5 = 0.331

4.575 x 1400  1000 

Now, E = 0.5863 − log  = 0.1026 volt
2 x 23,050  0.331 

e) If, as the result of the solution of MnO, the EMF of any cell becomes 0.05 volt more
positive, then

RT  aMnO . pH 2 
E − E0 = − ln
nF  aMn . pH 2O 
4.575 x 1400
0.05 = − log(aMnO ) at 1400K
2 x 23,050

log aMnO = −0.36 ⇒ aMn = 0.43

2) The EMF of the cell:

Ag ( s) | AgCl ( s ) | Cl2 (1 atm), Pt is found to be
E (volts ) = 0.977 + 5.7 x 10 −4 (350 − t ) − 4.8 x 10 −7 (350 − t ) 2
in the temperature range t = 1000C to t = 4500C.
Calculate the value of ∆C p for the cell reaction.

3) Calculate the EMF of the following cell at 250C.

Pt H 2 (1 bar) HCl(aq.) H 2 (0.1 bar with 0.9 bar of argon)
P
 P1  1
( )
SOLUTION: ∆G = RT ln 2  = 8.3145 x 298.15 ln 0.1 = – 5708 J / mol

But ∆G = −nFE
E = −∆G = 5708 = 0.0296V
nF 2 x 96,485

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

4) The reversible e.m.f. of a copper-zinc galvanic cell when measured was found to be
1.10V. Calculate the Gibb’s Free Energy change in this cell when 1 g ion of copper ions
is reduced to metallic copper and 1 g atom of metallic zinc is oxidized to its ions.

Solution: The overall cell reaction is given by Zn + Cu++ → Zn++ + Cu

Since copper and zinc are divalent, n = 2
Using the equation ∆G = −nFE = −2 X 96,494 X 1.10 J / g mole
But 4.184 joules = 1 calorie, so divide the above value with 4.184 to
convert into cal / g mole
∴ ∆G = −50,740 cal / g mole.

5) Calculate the e.m.f of a cell at 250C made of (a) standard zinc and copper electrodes, and
(b) zinc and copper electrodes, dipped into zinc sulphate solution of activity 0.1, and
copper sulphate solution of activity 0.01, respectively. Assume that any liquid junction
potential is negligible and standard electrode potentials of copper and zinc are +0.34 and
−0.76V respectively.

Solution:

(a) Since electrode potential of zinc is lower than that of copper, it will form the anode of
this cell. In this case the cell reaction is

At cathode: Cu+++2e → Cu E0 = +0.34)

At anode: Zn → Zn++ + 2e E0 = −(−0.76)*

We know that, the e.m.f. of the cell is the sum of the electrode potentials.
i.e. E0 = E0 of cathode + E0 of anode
= E0 of standard Cu electrode + E0 of standard Zn electrode
= +0.34 + [ −(−0.760] = 1.10 V

* Note: The potential which applies here is that of the oxidation reaction, that is, the
reduction potential with opposite sign.

(b) In this case the cell is given by

and overall reaction will be Zn + Cu++ → Cu + Zn++

RT a  RT  aZn .aCu + + 
∴ we have E = E0 + loge  reac tan ts  = E 0 + loge  
nF    a .a + + 
 a products  nF  Cu Zn 
E = 1.10 + (−0.0295) = 1.0705V

6) Calculate the e.m.f. of a copper concentration cell in which the activities of copper ions in
the two cells are 0.5 and 0.005 respectively (a) at 250C and (b) at 500C

Solution: Remember n = 2 for Cu

RT a  RT  0. 5 
E = log e  2  ⇒ E= loge  
nF a
 1 nF  0.005 
⇒ E = 0.0591 V at 250C and 0.0645 V at 500C

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

7) Calculate the equilibrium constant for the oxidation of ferrous ions by ceric ions,
Ce++++ + Fe++ → Ce+++ + Fe+++

Solution: The E0 of this reaction can be calculated as for galvanic cells; thus
E 0 = ECe
0 0
+ ( − E Fe ) = 1.61 + ( −0.77)
= 0.84 V at 255C
The equilibrium constant K for this reaction can be calculated using

RT 0.84
E0 = loge K ⇒ loge K = = 1.42
nF 0.0591

∴ K = 1014.2

8) The reaction of Cadmium-Calomel cell is represented by Cd + Hg2Cl2 = Cd2+ + 2Cl−

+2Hg, where all the components are present in their standard states. The reversible emf
(in volts) of the above cell varies with temperature as
E = 0.67 − 1.02 X 10 (T − 298) − 2.4 X 10 (T − 298) . Calculate the values of ∆G , ∆S0
0 −4 −6 2 0

and ∆H0 for the above reaction at 500C.

Solution: T = 50 + 273 = 3230K

Use ∆G0 = −nFE (where n = 2)
 dE 0   ∂ (∆G 0 )
Use ∆S 0 = nF   , Since   = − ∆S 0
 dT   ∂T  P
 dE 0 
Use ∆H = −nFE + nFT 
0 0
 , Since ∆G 0 = ∆H 0 − T∆S 0
 dT 
9) Calculate the equilibrium constant at 2980C for the following reaction if K=1.52 at 7000C
and the standard enthalpy change for the reaction is – 5.33 Kcal. (Given R=1.987
cal/deg/mole). Fe( s) + CO2 ( g ) = FeO( s) + CO( g )
d (ln K ) ∆H 0
Solution: We know that = , by integrating on both sides
dT RT 2
K  ∆H 0  1 1 
ln 2  = −  −  set K2 = 1.52 at 7000K and find K1 at 2980K
 K1  R  T2 T1 

10) Calculate the dissociation oxygen pressure of cuprous oxide in vacuum at 1000K. Given
Cu 2 O( s ) = 2Cu + 12 O2 ; ∆G 0 = 40,500 + 3.92T ln T − 29.5T cal.
Solution: Use ∆G 0 = − RT lnK, where K = p1/2 and T = 10000K

11) Calculate the equilibrium constant and equilibrium partial pressure of oxygen for the
0
reaction ZrO2 = Zr + O2; ∆G1727 0
C
= 259,940 + 4.33T ln T − 59.12T cal, if a vacuum of
10 −5 mm Hg at 17270C is used.

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

PROBLEM SET - 2
(Reversible Cells)

1. What is the standard emf of the electrochemical cell defined below? Standard reduction potentials: Cu2+ :
0.34 V, Mg2+ : −2.37 V.
Mg|Mg2+(1 mol.dm-3)||Cu2+(1 mol.dm-3)|Cu

Answer: 2.71 V

2. In which direction will the redox reaction shown below proceed spontaneously under standard conditions?
Standard reduction potentials: Fe3+ : 0.77 V, Cr3+ : −0.41 V
FeCl3(aq) + CrCl2(aq) FeCl2(aq) + CrCl3(aq)

Answer: Fe3+ + e- → Fe2+ has a greater reduction potential (0.77 V) than Cr3+ + e- → Cr2+ (-0.41 V). This
means that Fe3+ will oxidise Cr2+. The reaction will proceed from right to left.

3. Jyotsna wants to construct a cell by making use of the half-reactions: Au3+ + 3e- → Au and Cr3+ + 3e- →
Cr. Which metal (gold (Au), or chromium (Cr)) will be the cathode of this cell? Given, the standard
reduction potentials: Au3+ 1.51 V, Cr3+ −0.41 V.

Answer: The standard electrode potential of Au3+ (1.51 V) is greater than the standard electrode potential of
Cr3+ (−0.41 V). Reduction will take place at the gold electrode, which is the cathode.

4. Two half cells are Al3+/Al & Mg2+/Mg. Reduction potentials of these half cells are − 1.66 V & − 2.36 V
respectively. Write cell reaction and calculate cell potential.

Answer: Cell Reaction: 3Mg + 2Al3+ → 3Mg2+ + 2Al

EMF = − 1.66 − (− 2.36) = 0.7 V

5. What is the potential for the cell: Ag | Ag+(1.0 M) || Li+(1.0 M) | Li ? Given standard reduction potentials
of Li+ and Ag+ are −3.045 V and −0.799 respectively.

Answer: According to the convention of the cell, the reduction reaction is on the right. The cell on your left-
hand side is an oxidation process. Thus, add. E° = −3.844 V

6. In a galvanic cell, the anodic half-cell is mechanically kept replenished so that aZn+ 2 = 1 mol/lit. If current
ceases to flow calculate the activity and the concentration of copper ions in at 25°C.

Solution:

, which is very low

7. Using an electrochemical cell to measure the cell potential as a function of temperature at constant pressure
leads to a polynomial of type E = a + b(T − T0 ) + c(T − T0 ) 2 + d (T − T0 )3 , where T0 is the reference
temperature and a, b, c, and d are polynomial constants. Derive expressions for ∆G , ∆S , ∆H and C p .

∆G = −nFE ⇒ [
∆G = − nF a + b(T − T0 ) + c(T − T0 ) 2 + d (T − T0 )3 ]
Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW
Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

 ∂∆G   ∂E 
∆S = −  ⇒ ∆S = nF  
 ∂T  P  ∂T  P

∆H = ∆G + T∆S
 ∂S   ∂2E 
CP = T   ⇒ C P = nFT  2 
 ∂T   ∂T  P

2 3
8. A student applied equation E = a + b(T − T0 ) + c (T − T0 ) + d (T − T0 ) as continuous function in the
closed temperature interval [0ºC, 90ºC] or [273.15 K, 363.15 K] for plating silver (Ag) from silver chloride
(AgCl) according to the following redox (overall) reaction: 2 AgCl + H = 2 Ag + 2 HCl ( aq ) .

Calculate E 0 , ∆G 0 , ∆S 0 , ∆H 0 , Q and C Po at T = 250C.

Solution: If T = 25°C = 298.15 K, (T − T0 ) = 25 K , n = 2 and F = 96,500 C /mol = 96,500 J /mol V, then

the following are the results:

From E = a + b(T − T0 ) + c (T − T0 ) 2 + d (T − T0 )3 ⇒ E0 = 0.222 V

From ∆G = −nFE ⇒ ∆G 0 = −42,926 J/ mol <0
 ∂E 
From ∆S = nF   ⇒ ∆S 0 = −124.61J / mol.K <0
 ∂T  P
From ∆H = ∆G + T∆S ⇒ ∆H 0 = −80,000 J / mol <0
From Q = −T∆S ⇒ Q = ∆G − ∆H ⇒ Q = −37,152.47 J / mol <0
∂ E
2
From C P = nFT  2  ⇒ C P0 = 343 J / mol.K
 ∂T  P
These results indicate that Ag can be plated at T = 250C since E 0 > 0, ∆G 0 < 0, ∆S 0 < 0, ∆H 0 < 0 and
Qrev < 0 .

9. One-half of an electrochemical cell consists of a pure nickel electrode in a solution of Ni2+ ions; the other
half is a cadmium electrode immersed in a Cd2− solution. (a) If the cell is a standard one, write the
spontaneous overall reaction and calculate the voltage that is generated. (b) Compute the cell potential at
250C if the Cd2− and Ni2+ concentrations are 0.5 and 10−3 M, respectively. Is the spontaneous reaction
direction still the same as for the standard cell? The half-cell potentials for cadmium and nickel are −0.403
and −0.250 V respectively.

Solution: a) The cadmium electrode will be oxidized and nickel reduced because cadmium is lower in the
emf series; thus, the spontaneous reactions will be
Cd → Cd 2+ + 2e −
Ni 2+ + 2e − → Ni
________________________
Ni 2+ + Cd → Ni + Cd 2+ ⇒
0
ECell = E Ni 0
− ECd = −0.250 V −(−0.403 V) = + 0.153 V

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW

b) Let us assume that in contrast to part (a), nickel is oxidized and cadmium reduced according to
Cd 2+ + Ni → Cd + Ni 2+ .
RT  M 2n+ 
E = E0 + ln  ⇒ Here E 0 = ECd
0 0
− E Ni = −0.153 V
nF  M 1n+ 
0.0592  0.50 
E = −0.153 + ln −3  = −0.073V
2  10 
Since E is negative, ∆G > 0 , the spontaneous reaction direction is the opposite to that of Equation
Cd 2+ + Ni → Cd + Ni 2+ i.e. Ni 2+ + Cd → Ni + Cd 2+ . That is, cadmium is oxidized and nickel
is reduced.

10. Show that the activities are [M ] = [M ] in a galvanic cell, provided that the potentials is E = E
1
+2 +2
2
0
.

11. Show that ∆S = − R ln K in a galvanic cell at constant pressure.

Compiled by Dr. G. V. S. Nageswara Rao, Assistant Professor, MMED, NITW