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Question: Answered & Verified by Expert
If E ClO 3 - / ClO 4 - 0 = - 0 . 3 6  V  &  E ClO 3 - / ClO 2 - 0 = 0 . 3 3  V at 300 K.  The equilibrium concentration of perchlorate ion ClO 4 - which was initially 1.0 M in ClO 3 - when the reaction starts to attain the equilibrium,

2 ClO 3 - ClO 2 - + ClO 4 -

Given :  Anti log(0.509) = 3.329
ChemistryElectrochemistryJEE Main
Options:
  • A 0.0236 M
  • B 0.0190 M
  • C 0.123 M
  • D 0.191 M
Solution:
2424 Upvotes Verified Answer
The correct answer is: 0.191 M
The redox reaction can be split as

           Cl + 5 O 3 -1 Cl + 7 O 4 -1 + 2 e OHR - anode Cl + 5 O 3 -1 + 2 e Cl + 3 O 2 -1 RHR - cathode

     -------------------------------------------------------

       2 ClO 3 - 1 n = 2e - ClO 4 - 1 + ClO 2 - 1

E cell o = E red  cath o - E red  anode o

        = 0.33 - 0.36 = -0.03 V

as  E red  Anode o = E ClO 4 - 1 / ClO 3 - 1 o = + 0 . 3 6  V

      = - E ClO 3 - 1 / ClO 4 - 1 o

at equilibrium Ecell = 0

E cell o = 0 . 0 5 9 n log  K eq = 0 . 0 5 9 2 log  K eq

Writing concentration of speces at equilibrium

2 ClO 3 - 1 ClO 4 - 1 + ClO 2 - 1 1 - 2 x x x Molar Molar Molar

E cell o = - 0 . 0 3 = 0 . 0 5 9 2  log  x 2 1 - 2 x 2 = 0 . 0 5 9  log  x 1 - 2 x

- 0 . 0 3 0 . 0 5 9 = log x 1 - 2 x log 1 - 2 x x = 0 . 0 3 0 . 0 5 9

log 1 - 2 x x = 0 . 5 0 9

1 - 2 x x = 3 . 2 2 9

1 - 2x = 3.229 x 5.229x = 1

x = 1 5 . 2 2 9 = 0 . 1 9 1  M .

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