1.

Standard electrode potenital data are useful for understanding the suitablity of an oxidant in a redox titration. Some half cell reactions and their standard potential are given below: MnO_(4(aq))^(-) + 8H_((aq.))^(+) + 5e rarr Mn_((aq.))^(2+) + 4H_(2)O_(l),E^(@) = 1.51 V Cr_(2)O_(7(aq.))^(2-) + 14H_((aq.))^(+) + 6e rarr 2Cr_((aq.))^(3+) + 7H_(2)O_(l), E^(@) = 1.38 V Fe_(aq.)^(3+) 2e^(-) rarr Fe_((aq.))^(2), E^(@) = 0.77 V Cl_(2(g)) + 2e^(-) rarr 2Cl_((aq.))^(-), E^(@) = 1.40 V Identify the only incorrect statement regarding the quantitative estimation of aqueousFe(NO_(3))_(2):

Answer»

`MnO_(4)^(-)` can be used in aqueous `HCl`
`Cr_(2)O_(7)^(2-)` can be used in aqueous `HCl`
`MnO_(4)^(-)` can be used in aqueous `H_(2)SO_(4)`
`Cr_(2)O_(7)^(2-)` can be used in aqueous `H_(2)SO_(4)`

Solution :`MnO_(4)^(-)` will oxidise `Cl^(-)` ION according to equation.
`Mn^(7+) + 5e rarr Mn^(2+)`
`2CL^(-) rarr Cl_(2) + 2e`
Thus `E_(CELL)^(@) = E_(OP_(Cl^(-)//Cl_(2)))^(@) + E_(RP_Mn^(7+)//Mn^(2))^(@)`
`= -1.40 + 1.51 = 0.11 V`
or reaction is feasible.
`MnO_(4)^(-)` will oxidise `Fe^(2+)` to `Fe^(3+)`
`Mn^(7+) + 5e rarr Mn^(2+)`
`Fe^(2+) rarr Fe^(3+) + E`
`E_(cell)^(@) = E_(OPFe^(2+)//Fe^(3+))^(@) + E_(RPMn^(7+)//Mn^(2+))^(@)`
`= -0.77 + 1.51 = 0.74 V`
or reaction is feasible.
Thus `MnO_(4)^(-)` will not oxidise only `Fe^(2+)` to `Fe^(3+)` in aqueous `HCl` but it will also oxidise `Cl^(-)` to `Cl_(2)`. Suitable oxidant shoould not oxidise `Cl^(-)` to `Cl_(2)` and should oxidise only `Fe^(2+)` to `Fe^(3+)` in redox titration.


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