Taken from Basuchandra’s Engineering Chemistry Textbook authored by

Dr. Chandra Shekara. B. M. and Dr. Basavaraju. B. C, BIT

MODULE- I-ELECTROCHEMISTRY AND ENERGY STORAGE SYSTEMS

Numerical problems on E, Eo, Ecell, Ecell of Electrolyte concentration cell.
1. Calculate the EZn2+/Zn at 28oC. Given that standard potential of Zn electrode is -0.76 V and
[Zn2+] is 0.25 M.
Nernst equation for single electrode potential is E  Eo 
2.303 R T
nF

log Mn  
2.303 R T
EZn / Zn 2   EoZn / Zn 2  
nF
log Zn2   
2.303  8.314  301
  0.76  log 0.25
2  96500
 0.78 V

2. Calculate the Eocu2+/cu, if the potential of Cu electrode immersed in 0.015 M Cu 2+ solution is

0.296 V at 25oC.
Nernst equation for sin gle electrode potential is E  Eo 
0.0591
n
 
log Mn  at 298 K.

o
ECu / Cu 2
0.0591
 ECu / Cu 2 
n

log Cu 2  
0.0591
 0.296  log 0.015
2
 0.35 V

3. A galvanic cell is obtained by the combination of Fe rod immersed in ferrous sulphate

solution of concentration 0.25M and Cu rod immersed in copper sulphate solution of
concentration 0.45M. Give cell representation, cell reactions and calculate EMF of cell at
30oC. Given that standard potentials of Cu and Fe electrodes are 0.34 and − 0.41 V
respectively.
Potential of Cu electrode is greater than Fe electrode, hence Fe is taken as anode and Cu is
taken as cathode.
Representation of cell is
Fe│Fe2+││Cu2+│Cu
Cell reactions are
Anode : Fe  Fe 2   2e
Cathode : Cu2   2 e   Cu
Overall reaction : Fe  Cu2   Fe 2   Cu
EMF of galvanic cell is
 Taken from Basuchandra’s Engineering Chemistry Textbook authored by
Dr. Chandra Shekara. B. M. and Dr. Basavaraju. B. C, BIT

Ecell  Eocell 
2.303 R T
log
M n
at cathode  where E
o
 Eocathode  Eanode
o

nF M n
at anode  cell


o
 ECu  EoFe  
2.303 R T
log
Cu2   
2F Fe 2   
 0.34   0.41 
2.303  8.314  303
log
0.45
2  96500 0.25
 0.758 V

4. A galvanic cell is formed by the combination of Zn rod immersed in zinc chloride solution of
concentration 0.5M and Li rod immersed in Lithium chloride solution of concentration 0.15M.
Give the cell representation, cell reactions and calculate EMF of cell at 25oC. Given that
standard potentials of Li and Zn electrodes are -3.04 and − 0.76 V respectively.
Potential of Zn electrode is greater than Li electrode, hence Li is taken as anode and Zn is
taken as cathode.
Representation of cell is Li│Li+││Zn2+│Zn
Cell reactions are


Anode : Li  Li   e   2 
2 
Cathode : Zn  2 e  Zn
Overall reaction : 2 Li  Zn2   2 Li   Zn

EMF of galvanic cell is

Ecell  Eocell 
0.0591
log
M n
at cathode  at 298 K where E o
 Eocathode  Eanode
o

n M n
at anode  cell


 EoZn  EoLi   0.0591
log
Zn 
2

2 Li 
 2

  0.76   3.04  
0.0591
log
0.5
2 0.15 2
 2.32 V

Note…
In general, electrode with lower standard potential (E o) is taken as anode and electrode with
higher standard electrode potential is taken as cathode, so that E o of cell is positive. The value
of ‘n’ and concentration of metal ions at cathode and anode in Nernst equation should be
decided from overall cell reaction. The value of ‘n’ is the total number of electrons released at
anode or consumed at cathode in the balanced net cell reaction. To decide concentration of
ions, if two metal ions are present in overall reaction, then concentration is squared and if
three metal ions are present in overall reaction, then concentration should be cubed in the
Nernst equation.
 Taken from Basuchandra’s Engineering Chemistry Textbook authored by
Dr. Chandra Shekara. B. M. and Dr. Basavaraju. B. C, BIT

5. Calculate the decrease in free energy of the cell reaction that occurs in a galvanic cell,
Mg│MgCl2(0.5M)││AuCl3(0.25M) │Au , at 30oC. Given that standard potentials of Mg and Au
electrodes are −2.37 and 1.50V respectively.
Cell reactions are
Anode :  Mg 
 Mg 2  2 e    3
Cathode :  Au 3  3 e  
 Au   2
Overall reaction : 3 Mg  2 Au 3 
 3 Mg 2  Au
Decrease in free energy during cell reaction in a galvanic cell is given by the equation,
 ΔG  nFEcell

2.303  R  T  M n  at cathode 
Ecell  Ecell
o

nF
log  n 
 M at anode 
 where E
o
cell  Ecathode
o
 Eanode
o


2.303  8.314  303  Au 3  2


 E E o
Au
o
Mg  
6  96500
log
 Mg 2  3

0.25
2

 1.5   2.37    0.01 log

0.5 3
 3.87  0.003  3.867 V

 ΔG  nFEcell
 6  96500  3.867  2238.9 kJ

NUMERICAL PROBLEMS ON ELECTROLYTE CONCENTRATION CELL

1. A galvanic cell is obtained by combining two Zn electrodes immersed in Zinc sulphate

solutions of concentrations 0.05 and 0.25M at 30 oC. Give the cell representation, cell
reaction and calculate EMF of cell.
Both electrodes in cell are made of same metal immersed in same electrolyte solution but
of different concentrations. Hence it is an electrolyte concentration cell.
Cell representation is Zn│ZnSO4(0.05M)││ ZnSO4(0.25M) │ Zn
2 
At anode Zn 
 Zn (0.05)  2e
2
At cathode Zn(0.25)  2e  
 Zn
2 2
Overall reaction Zn(0.25) 
 Zn(0.05)
EMF of cell
 M n  at cathode  2.303  8.314  303
log  n 
2.303 R T 0.25
Ecell   log
nF  M at anode  2  96500 0.05
Ecell  0.02 V .
 Taken from Basuchandra’s Engineering Chemistry Textbook authored by
Dr. Chandra Shekara. B. M. and Dr. Basavaraju. B. C, BIT

2. EMF of the cell Cu|CuSO4 (0.01)||CuSO4(X)|Cu at 300 K is 0.015. Find the concentration of
CuSO4 at cathode.
EMF of a concentration cell is given by
2.303 R T  M n  at cathode  2.303 R T Cu 2 at cathode 
Ecell  log  log
nF  M n  at anode  nF Cu 2 at anode 
 E n F 
 Cu 2 at cathode   Cu 2 at anode   Anti log  cell 
 2.303  R  T 
 0.015  2  96500 
 0.01 Anti log 
 2.303  8.314  300 
 0.319 M .
3. Hg│Mercurous sulphate(0.01M)││Mercurous sulphate(0.1M)│Hg at 29oC is 0.03V. Find the
valency of mercurous ion.
E M F of a concentration cell is given by

2.303 R T  M n  at cathode 
E cell  log
n F  M n  at anode 

2.303 R T  M n  at cathode 
n  log
E cell  F  M n  at anode 


2.303  8.314  302
log
 0.1
0.03  96500  
0.01
n  2
M ercurous ion is found to occur as H g 22  ion .
1. EMF of the cell Ag|AgNO3(C1)|| AgNO3(C2 = 0.2)|Ag is 0.8 V. Calculate C1 of the cell.
(3m) Ans: 0.3498 V
2. Represent the cell formed by the coupling of two copper electrodes immersed in cupric
sulphate solutions. Concentration of cupric ions in one electrode system is 100 times more
concentrated than the other. Write the cell reaction and calculate the potential at 300 K. (5m)
Ans: 0.0595 V
3. What are concentration cells? Calculate cell potential of the following cell at 298K
Ag|Ag+(0.001M)||Ag+(0.50M)|Ag. What will be the potential, when the concentration of silver ions
in the above cell is changed from 0.001M to 0.005M at same temperature? (4m) Ans: 0.159 V
and 0.1182 V
4. A concentration cell was constructed by immersing two silver electrodes in 0.05M and 0.1M
AgNO3 solution. Write cell representation, cell reactions and calculate emf of the
concentration cell. (6m) Ans: 0.0178 V
5. The spontaneous galvanic cell Tin|Tin ion (0.024M)|| Tin ion (0.064M)|Tin develops an EMF of
0.0126 V at 25oC. Calculate the valency of tin. (4m) Ans: 2
 Taken from Basuchandra’s Engineering Chemistry Textbook authored by
Dr. Chandra Shekara. B. M. and Dr. Basavaraju. B. C, BIT

MODULE-III
Chemical Fuels
Numerical problems on GCV and NCV
1. Calculate the gross calorific value and net calorific value of a sample of coal. 0.5 g of which
when burnt in a bomb calorimeter raised the temperature of water from 293K to 296.4K. The
mass of water is 1000 g and water equivalent of calorimeter is 350 g. The specific heat of
water is 4.187 kJ/kg/K, latent heat of steam is 2454 kJkg-1. The coal sample contains 93%
carbon, 5% hydrogen and 2% ash.
Mass of the fuel, m = 0.5 g = 0.5 × 10−3 kg
Mass of water taken, W = 1000 g = 1000 × 10−3 kg
Water equivalent of calorimeter, w = 350 g = 350 × 10 −3 kg
Initial temperature of water, t 1o C = 293 K

Final temperature of water, t 2o C = 296.4 K

Specific heat of water, s = 4.187 kJ kg-1K-1

Latent heat of steam, L = 2454 kJ/kg

 W  w   t2  t1   s
GCV  J Kg 1
m
= (1000 +350) × 10−3 kg  (296.4 -293)K  4.187 kJ kg-1K-1
0.5 × 10−3 kg
= 1350 × 10−3 kg  3.4 K  4.187 kJ kg-1K-1
0.5 × 10−3 kg
= 38436.66 kJ kg-1
NCV =  GCV - latent heat of condensation of water 


=  GCV - 0.09 × % of H 2 in fuel × L 
  
= 38436.66 kJ kg-1 - (0.09  5)  2454 kJ kg-1
= 38436.66 kJ kg-1– 1104.3 kJ kg-1
= 37332.36 kJ kg-1
2. When 0.6 g of solid fuel having gross calorific value of 43500 kJkg -1 is burnt in calorimeter
the temperature of water raised from 24oC to 28.5oC. The mass of water is 1100g. Calculate
water equivalent of calorimeter.
The specific heat of water is 4.187 kJ/kg/K, latent heat of steam is 2454 kJkg-1.
m = mass of the fuel = 0.6 g = 0.6 × 10−3 kg
 Taken from Basuchandra’s Engineering Chemistry Textbook authored by
Dr. Chandra Shekara. B. M. and Dr. Basavaraju. B. C, BIT

W = mass of water taken = 1100 g = 1100 × 10−3 kg

w = water equivalent of calorimeter = ……kg
t1 = initial temperature of water = 24oC= 297 K
t2 = final temperature of water = 28.5oC =301.5 K
s = specific heat of water = 4.187 kJ kg-1K-1
L = Latent heat of steam = 2454 kJ/kg.
 W  w    t 2  t1   s
GCV  J Kg 1
m
GCV  m
 W  w 
 t 2  t1   s
GCV  m
w W
 t 2  t1   s
43500  103  0.6  103
  1.1
4.5  4.187  103

 1.385  1.1  0.285 Kg .

1. Calculate the gross and net calorific value of a sample of coke from the following data.
Mass of coke = 0.795 × 10−3 kg
Mass of water = 2.5 kg
Water equivalent of calorimeter = 1.3 kg
Specific heat of water = 4.187 KJ/kg/K
Rise in temperature = 1.8 K
% of hydrogen in the fuel sample = 2.5
Latent heat of steam = 587 Cal/g

Ans: GCV = 36024 KJ/Kg NCV = 35471 KJ/Kg

Hint: 587 cal/g = 587 × 4.187 KJ/Kg
2. Calculate the gross and net calorific value of a sample of coal from the following data.
Mass of coke = 0.98 g
Mass of water = 2600 g
Water equivalent of calorimeter = 368 g
Specific heat of water = 4.187 J/g/K
Rise in temperature = 2.8 K
 Taken from Basuchandra’s Engineering Chemistry Textbook authored by
Dr. Chandra Shekara. B. M. and Dr. Basavaraju. B. C, BIT

% of hydrogen in the fuel sample = 5.8

Latent heat of steam = 2454 J/g
Ans: GCV = 35505.76 KJ/Kg NCV = 34224.77KJ/Kg

3. Define gross and net calorific value. Calculate the gross and net calorific value of a sample
of coke from the following data.
Mass of sample = 0.85 × 10−3 kg
Mass of water = 2.35 kg
Water equivalent of calorimeter = 0.45 kg
Specific heat of water = 4.187 KJ/kg/K
Rise in temperature = 3.2oC
% of hydrogen in the fuel sample = 2.5
Latent heat of steam = 2457 kJ/kg
Ans: GCV = 44135.90 KJ/Kg NCV = 43583.07 KJ/Kg

4. On burning 1.15 g of a solid fuel, in a bomb calorimeter, the temperature of 3.5 kg of water
was increased by 26.5oC to 28.5oC. Water equivalent of the calorimeter is 325 g. Specific heat
of water is 4.187 j/g/K and latent heat of steam is 2458 J/g, respectively. If the fuel contains
4% of hydrogen, calculate its gross and net calorific values.
Ans: GCV = 27852.65 KJ/Kg NCV = 26967.77 KJ/Kg

5. On burning 0.96 × 10−3 kg of a solid fuel, in a bomb calorimeter, the temperature of 3.5 kg of
water was increased by 2.7oC. Water equivalent of the calorimeter and latent heat of steam
are 0.385 kg and 2455 kJ/kg, respectively. If the fuel contains 5% of hydrogen, calculate its
gross and net calorific values.
Ans: GCV = 45749.51 KJ/Kg NCV = 44644.76 KJ/Kg