184 Modern Approach to Chemical Calculations

1
K1  x (1)
50
1
For solution B: sp. conductance K2   x. (2)
100
When equal volumes of A and B are mixed, both the solutions get doubly
diluted; hence their individual contribution towards the sp. conductance
K1 K2
of the mixture will be and respectively and the sp. conductance of
2 2
1
the mixture will be K1 K2 .
2
1 1
for the mixture: K1 K2   x. (3)
2 R
(R is the resistance of mixture)
From eqns. (1), (2) and (3), we get R  6667 ohms.

Ex. 35. In a conductivity cell the two platinum electrodes, each of area 10 sq cm,
are fixed 15 cm apart. The cell contained 005 N solution of a salt. If the two
electrodes are just half dipped into the solution which has a resistance of
50 ohms, find equivalent conductance of the salt solution.
Solution : Since the electrodes of the cell are just half dipped, the effective
area will be 5 sq cm.
l 15
Cell constant    03 cm  1.
a 5
Specific conductance  conductance  cell constant
1
  cell constant
resistance
1 3
  03  mho cm  1.
50 500
Equivalent conductance  specific conductance  volume (Eqn. 8)
3
  20000  120 mho cm2.
500
(005 N = N/20 V = 20,000 cc)

Ex. 36. A big, irregular-shaped vessel contained water, the sp. conductance of which
was 256  10  5 mho cm  1. 500 g of NaCl was then added to the water and
the sp. cond. after the addition of NaCl, was found to be
310  10  5 mho cm  1. Find the capacity of the vessel if it is fully filled with
water. ( NaCl  1499
Solution : Let the volume of the vessel be V cc.
wt. in grams
Number of equivalent of NaCl 
eq. weight
 Electrolysis and Electrolytic Conductance 185

500
  8547.
585
V
volume of water (cc) containing 1 eq. of NaCl  
8547
The sp. cond. of the NaCl solution (only due to presence of Na+ and
Cl  ions)
 310  10  5  256  10  5
 054  10  5.
V
NaCl  054  10  5 
 (Eqn. 8)
8547
Since the vessel is big, the resulting solution may be supposed to be
dilute.
NaCl  NaCl

V
054  10  5   1499
8547
V  237  108 cc.

Ex. 37. The equivalent conductance of 010 N solution of MgCl2 is 971 mho
cm2 eq.  1 at 25 C. A cell with electrodes that are 150 cm2 in surface area and
050 cm apart is filled with 01 N MgCl2 solution. How much current will flow
when the potential difference between the electrodes is 5 volts?

050 1
Solution : Cell constant   
150 3
equivalent conductance
Specific conductance  (Eqn. 8)
volume cc containing 1 eq.
971
 (for 01 N solution V=10,000 cc)
10,000
 000971 mho cm  1.
Conductance  specific conductance/cell constant
(Eqn. 7)
000971
  002913 mho.
1/3
1
resistance  ohm.
002913
potential difference volt
current in amp  (Ohm’s law)
resistance ohm
5
  01456 ampere.
1/002913
186 Modern Approach to Chemical Calculations

Ex. 38. A 001 D* solution of KCl has a specific conductance value of

000141 mho cm  1. A cell filled with this solution has a resistance of
42156 ohms.
(a) What is the cell constant?
(b) The same cell filled with a solution of HCl has a resistance of 10326 ohms.
What is specific conductivity of the HCl solution?
specific conductance
Solution : (a) Cell constant 
conductance
specific conductance

1/resistance
000141
  000594 cm  1.
1/42156
1
(b) Conductance of HCl solution  mho.
10326
Since the same cell is used, we shall take the same value of cell constant
in this case.
Sp. conductance  cell constant  conductance
1
 000594 
10326
 000575 mho cm  1.

Ex. 39. The equivalent conductance at infinite dilution are sodium benzoate  824;
hydrochloric acid  4262 and sodium chloride  1265 mho cm2. Calculate for
benzoic acid.
Solution : From Kohlrausch’s law, we get,
benzoic acid  sod. benzoate hydrochloric acid  sodium chloride
 824 4262  1265
 3821 mho cm2.

Ex. 40. At 18 C the mobilities of NH4 and ClO4 ions are 66  10  4 and
57  10  4 cm2 volt  1 s  1 at infinite dilution. Calculate equivalent conductance
of ammonium chlorate solution.
Solution : From Kohlrausch’s law, we have,
NH4ClO4 

NH4 ClO4

 FU NH4 FU 
ClO4 (Eqn. 11)
 F U NH4 U 
ClO4 
4
 96500 66  10 57  10  4
 11867 mho cm2.
* A one demal (1 D) solution contains 1 mole of salt in 1 litre solution at 0 C.
 Electrolysis and Electrolytic Conductance 187

Ex. 41. For H and Na the values of are 3498 and 5011 respectively. Calculate
the mobilities of these ions and their velocities if they are in a cell in which the
electrodes are 5 cm apart and to which a potential of 2 volts is applied.
Solution : We have
H 3498
U H  
F 96500
 362  10  3 cm2 volt  1 s  1
Na 5011
U Na  
F 96500
 520  10  4 cm2 volt  1 s  1
Further, we know that
ionic velocity cm/s
U 
pot. diff. volt / distance between the electrodes cm
(Eqn. 12)
2
velocity of H  362  10  3 
5
 145  10 cm s  1.
3

2
Velocity of Na  520  10  4 
5
 208  10 cm s  1.
4

Ex. 42. The equivalent conductance of an infinitely dilute solution of NH4Cl is 150
and the ionic conductances of OH  and Cl  ions are 198 and 76 respectively.
What will be the equivalent conductance of the solution of NH4OH at infinite
dilution. If the equivalent conductance of a 001 N solution of NH4OH is 96, what
will be its degree of dissociation?

Solution : NH4Cl  NH4 Cl



NH4  NH4Cl  Cl
  150 – 76  74

NH4OH  NH4 OH
  74 198  272
Further,
c
degree of dissociation  (Eqn. 9)

96
  00353.
272

Ex. 43. Calculate the dissociation constant of water at 25 C from the following data:
Specific conductance of H2O  58  10  8 mho cm  1
H  3500 and OH
  1980 mho cm2
188 Modern Approach to Chemical Calculations

Solution : Suppose water contains X moles per litre (or X eq./L) of H ions

(or OH ions).
B X equivalents of H ions are produced from X eq. of water
volume (cc) containing 1 eq. of water which dissociated into its ions
1000
 
X
eq. conductance of water  sp. cond.  V
1000
 58  10  8  
X
Since water dissociates feebly, i.e., water may be considered to be a dilute
solution of H and OH  ions,
H2O  H2O  H OH
 .
1000
58  10  8   350 198  548.
X
X  10  10  7.
[H ]  [OH  ]  1  10  7.
For the equilibrium,
H2O  H OH 
[H ] [OH  ]
Equilibrium constant K 
[H2O]
Kw  K  [H2O]  [H ] [OH  ]
 10  10  7  10  10  7  1  10  14.
Kw 1  10  14
K   18  10  16 mole/litre.
[H2O] 555
1000
[H2O]   555 moles/litre
18

Ex. 44. Calculate Ka of acetic acid if its 005 N solution has equivalent conductance
of 736 mho cm2 at 25 C.  CH3COOH  3907

c 736
Solution : Degree of dissociation (x)    00188.
3907
For the equilibrium
005 0 0 Initial concn. moles litre
CH3COOH  CH3COO  H
005 1  x 005 x 005 x Equilibrium concentration
(for CH3COOH, 005 N  005 M)
005x  005x
Ka 
0051  x
 Electrolysis and Electrolytic Conductance 189

Since x is very small,

Ka  005x2  005  001882
 176  10  5 .mole/litre.

Ex. 45. The specific conductance of a saturated solution of AgCl at 25 C after

subtracting the specific conductance of conductivity of water is 228  10  6 mho
cm  1 . Find the solubility product of AgCl at 25 C.
 AgCl  1383 mho cm2

Solution : For equilibrium,

AgCl  Ag Cl 
Ksp  [Ag ] [Cl  ]
If the solubility of AgCl in water is, say, x moles/litre or x eq./L,
Ksp  x  x  x2.
1000
volume containing 1 eq. of AgCl 
x
AgCl  sp. cond.  V
1000
 228  10  6  
x
Since AgCl is sparingly soluble in water, AgCl  AgCl  1383.
1000
228  10  6   1383
x
or x  1644  10  5 eq./litre or mole/litre.
Ksp  x2  1644  10  5 2
 270  10  10 (mole/litre)2.

PROBLEMS
(Answers bracketed with questions)

1. Molten AlCl3 is electrolysed with a current of 05 amp to produce 270 g Al.
(i) How many g eq. of Al were produced? (ii) How many gram-atoms of Al were
produced? (iii) How many atoms of Al were produced? (iv) How many electrons
were required? (v) What is the no. of faradays of electricity consumed? (vi) How
long did the electrolysis take place? (vii) How many litres of Cl2 at NTP were
produced?  i 3 g eq ii 1 iii  Av. constant iv 3  Av. constant

v 3 F vi 160 h 50 min vii 336 litres
2. In the electrolysis of an aqueous Cr2SO43 solution using a current of 2 amp, the
mass of cathode is increased by 8 g. How long was electrolysis conducted?
(619 h)