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ELECTRO CHEMISTRY
P -1
1.(a)Define molar conductivity of a substance and describe how for weak and
strong electrolytes, molar conductivity changes with concentration of solute. How
is such change explained? .
(2009,2012, Delhi - 2012)
Ans : Molar conductivity : the conductivity of a solution having one mole of
electrolyte, placed between two electrodes separated by 1 cm apart and having
area of cross section as 1 cm.
Molar conductivity increases sharply for weak electrolyte with decrease in
concentration because both number of ions as well as mobility of ions increases
with dilution.i.e. decrease in concentration where as in case of strong
electrolyte , it increases slightly on dilution because number of ions do not
increase appreciably where as mobility of ions increases.
(b) Define conductivity & limiting molar conductivity of an electrolyte. Discuss
the variation of conductivity with concentration.
Ans : When a solution is placed between two electrodes which is 1 cm apart
and having area of cross section 1 squre cm then it is called conductance.
Geater the number of ions, more is the conductance. On dilution, number of
ions per unit volume decreases,hence conductivity decreases.
When concentration approaches zero, the molar conductivity is known as limiting
molar conductivity and is represented by the symbol m .
2. State the relationship amongst the cell constant of a cell, the resistance of the
solution in the cell and the conductivity of the solution. How is molar conductivity
of a solute related to the conductivity of its solution?
(2009,2011,2012)
=kx
1000
C
conductivity
3.What type of a cell is the lead storage battery? Write the anode and the
cathode reactions and the overall reaction occurring in a lead storage battery
while operating.(2009,2010,2011,2012)
Ans : Lead storage battery is a secondary battery .The cell reactions when the
battery is in use are given below:
At Anode
At Cathode
i.e., overall cell reaction consisting of cathode and anode reactions is:
Pb(s)+PbO(s)+2HSO(aq) 2PbSO(s) + 2HO(l)
On charging the battery the reaction is reversed i.e. PbSO(s) deposited on the
electrode (anode and cathode )is converted back into Pb & PbO and HSO is
regenerated.
4. (a)Suggest two materials other than hydrogen that can be used as fuels in
fuel cells.
P -2
(b) write its one important characteristic.
(c) What is sacrificial protection of Iron .
(d) Metallic and electrolytic conductor
(e)Two difference between electro chemical cell & electrolytic cell .
(f) Two difference between E.M.F. & potential difference .
1
2
Metallic conductor
Flow of electricity takes place
without the decomposition of
material
Flow of electricity is due to flow of
electron
Electro chemical cell
It converts chemical energy into
electrical energy
Anode &cathode are immersed in
two separate compartments
joined by a salt bridge.
E.M.F.
It is the difference of potential
between two electrodes when no
current is flowing through the
circuit.
It is responsible for the flow of
steady current through the circuit.
Electrolytic conductor
Flow of electricity takes place by the
decomposition of material
Flow of electricity is due to flow of
ions.
Electrolytic cell
It converts electrical energy into
chemical energy
Both the electrodes are immersed in
same solution.
Potential difference
It is the difference of potential
between two electrodes when
current is flowing through the circuit.
It is not responsible for the flow of
steady current through the circuit.
HCO
2 H + CO
E(Fe/Fe) = 0.44 V
These electrons reach another spot H ions and dissolved oxygen take up these
electrons and this place work as cathode.
At Cathode : O(g) + 4 H(aq) + 4 e 2 HO (l )
=1.23 V
EH/ O / H O
+ x HO
P-3
cathode
Ag
anode
Ag
Ag
Ag
Ag
4OH
Ag +e
(ii)
Ag
Ag + e
2 H + 2e
4OH
Cu
Cl
(iv)
Cu + 2e
Cu
2Cl
Cl + 2e
Na
Cl
Cl
(v)
Na + e
Na
2Cl
2Cl
Cl + 2e
(vi)
2 H + 2e
Cl + 2e
8. Give reasons:
(i)Rusting of iron is faster in saline water than in ordinary water.
Ans- Saline water contains NaCl. This NaCl helps water to dissociate into H and
OH. Greater the number of H ion ,quicker will be rusting.
(ii)An electrochemical cell stops working after sometime.
Ans- Due to the decrease of concentration of Anodic half cell and increase of
concentration in cathodic half cell,the reduction potential in anodic half cell
decreases and cathodic half cell increases. But at a certain time, it becomes
equal and so flow of current is stopped.
(iii) Porous plate or salt bridge is not required in a lead storage cell.
Ans- Porous plate or salt bridge is required, when oxidising agent and reducing
agent is in liquid state.But in lead storage battery, the oxidising agent (PbO),
reducing agent (Pb) as well as product of redox reaction (PbSO) are solid.Hence
Porous plate or salt bridge is not required
(iv) Direct current is not used in measuring electrolytic conductance.
It is because direct current causes electrolysis of the electrolytic solution due to
which concentration near the electrode changes.
(v) A mercury cell gives constant voltage through out its life
P -4
Ans- The over all reaction of this cell does not contain any ion in
solution.Hence,concentration remains same and therefore voltage.
9. Formulate the Galvanic cell in which the following reaction takes place :
Zn + Ag
Zn + 2Ag
(2008)
State : (i) Which one of its electrodes is negatively charged .
NUMERICALS
1. (i) The conductivity of a 0.20 M solution of KCl at 298 K is 0.0248 S cm.
Calculate its molar conductivity.
Ans
: 124.0 S cm mol
(2008)
(ii) The molar conductivity of a 1.5 M solution of an electrolyte is found to
be 138.9 S cm mol . Calculate conductivity of this solution. Ans : 0.208 S
cm
(2012)
(iii)The resistance of a conductivity cell containing 0.001 M KCl solution at 298
K is 1500 . What is the cell constant if the conductivity of 0.001 M KCl solution
at 298 K is 0.146 10 S cm?
Ans : 0.219
(2008 , Delhi -2012)
(iv) The electrical resistance of a column of 0.05 M NaOH solution of diameter 1
cm and length 50 cm is 5.55
mol(2012)
2.(i) Conductivity of 0.00241 M acetic acid solution is 7.896
105
S cm.
Calculate its molar conductivity in this solution. If m for acetic acid be 390.5 S
cm mol, what would be its dissociation constant? Ans : 32.8 S cm mol,
Ka
= 1.86 10
(2008)
(ii)
3.(i) How many mercury moles would be produced by electrolysing 0.10 M
[Hg(NO)] solution with a current of 2 ampere for 3 hours
[Hg = 200.6 g mol-I]
Ans : 0.11
(2010)
P -5
(ii)Three electrolytic cells A, B and C containing solutions of zinc sulphate, silver
nitrate and copper sulphate respectively, are connected in series. A steady
current of 1.5 ampere was passed through them until 1.45 g of silver was
deposited at the cathode of cell B. How long did the current flow? What mass of
copper and what mass of zinc were deposited in the concerned cells?
(Atomic masses of Ag = 108, Zn = 65.4, Cu = 63.5)
Ans : 14.4 mt , 0.426 gram , 0.438 gram
(2008)
4. (i) Calculate the cell voltage for the following Voltaic cell which is set up at
25C :
(a)
E cell
= 0.46 V )
Ans: 0.3125 V
(2009,2012)
(b)Al | Al (0.001 M) and Ni | Ni (0.50 M) [
N i 2 +/
E
= 0.25 V ,
E Al / Al
- 1.66 V ]
Ans : 1.4602 V
(2009)
(c) Pt(s)|Br(l)|Br(0.010 M)||H(0.030 M)| H(g) (1 bar)|Pt(s).
(ii) Calculate the potential for half-cell containing 0.1 M
Cr(aq) ,and 1.0 x
Cr 2 O7
104
E = 1.315 V
K 2 Cr 2 O7 (aq) , 0.2 M
Ans
: 0.782V
and the standard electrode potential is given as E = 1.33 V
(2011)
(iii) A Voltaic cell is set up at 25C with the following half cells Al(0.001 M)
and Ni (0.50M) . Write an equation for the reaction that occurs when the cell
generates an electric current and determine the cell potential. (Given E Ni/Ni
= - 0.25 V E Al/ Al = - 1.66 V)
Ans : 1.88V
(2011)
(iv) Calculate the cell potential , E at 25C for the cell if the initial concentration
of Ni(NO) is 0.1 molar and the initial concentration of AgNO is 1.0 molar .
+/ Ag
Ag
= 0.80V , Log 10 = 1)
Ans :
(2012)
Ag
= 0.80V)
(2012)
Cd2 +/Cd
E
= - 0. 40 V ,
Fe(aq) + Cd(s)
E Fe /Fe
= -0.44 V ]
Ans : 22.57
(20O9)
(b) Ni(s) + 2Ag(aq) Ni(aq) + 2Ag(s)
(2011)
E = 1.05 V
( 1 F = 96500 C mol)
(c) In a button cell , widely used in watches , the following reaction takes place
:
Zn(s) + AgO(s) + HO
Z n2+ /Zn
E
= - 0.76 V ,
A g +/ Ag
E
Z n2+ /Zn
E
= - 0.76 V ,
A g +/ Ag
E
= +0.80 V]
(2009)
(ii) A copper-silver cell is set up. The copper ion concentration is 0.10 M. The
concentration of silver ion is not known. The cell potential when measured was
+/ Ag
E Cu
/Cu
Ag
= 0.34V) (2010)
2Ag + 2e
2Ag
E =
0.80 V
Anodic half cell reaction:
Cu
2e
Cu
0.34 V
................................................................................................................................
................................................................
Net cell reaction
2Ag + Cu
Cu E = 1.14 V
Let [ Ag] = x M
Q=
2+
Cu
+
Ag
[ Ag ]2 .
(0.1)
(x)
2Ag +
0.0591
n
Or
Or
0.422 = 1.14
0.1
x
0.0591
2
= Antilog 24.3
log
0.1
x
log Q
i.e. log
Hence x = 7.1 x
0.1
x
102
= 24.3
M.
91
m NaCl + m HCl
7. Two half cell reaction of an electrochemical cell are given below : (2011)
MnO + 8H + 5e
Sn (aq) 2e
Mn + 4HO
4 +
Sn
(aq)
E = + 1.51 V ;
E = + 0.15 V
Construct the redox equation from the two half cell reactions and predict if this
reaction favours the formation of reactants and products shown in the equation .
Ans : net cell reaction : 2MnO + 16H + 5 Sn (aq) --------> 2 Mn + 8HO +
(aq)
4+
5 Sn
E = 1.66V