1.

State and explain Kohlrausch's law ofindependent migration of ions.

Answer»

Solution :Statement of Kohlrausch's LAW: This statesthat of INFINITE dilutionof the solution,each ionof an electrolytemigratesindependentlyof its co-ionsand contributesindependentlyto thetotalmolarconductivityof the electrolyte, irrespectiveof the natureof otherions presentin te solution .
Explanation :Both theions, cationand anionof the electrolytemake a definitecontributionto the molar conductivity ofthe electrolyte at infinite dilution or ZERO concentration`(wedge_(0))`.
Of `lambda_(+)^(0)` and `lambda_(-)^(0)`are the molarconductivities of cation and nation respectively at infinite dilution, then
`wedge_(0) = lambda_(+)^(0) + lambda_(-)^(0)` .
This is known as Kohlrausch's law of independentmigrationof ions.
`wedge_(0KCl) = lambda_(K^(+))^(0) + lambda_(Cl^(-))^(0)` and `wedge_(0NaCl) = lambda_(Na^(+))^(0) + lambda_(Cl^(-))^(0)`
`:. wedge_(0KCl) - wedge_(0NaCl)`
`= (lambda_(K^(+))^(0) + lambda_(Cl^(-))^(0)) - (lambda_(Na^(+))^(0) + lambda_(Cl^(-))^(0)) = lambda_(K^(+))^(0) - lambda_(Na^(+))^(0) + lambda_(I^(-))^(0)`
`:. wedge_(0KI) - wedge_(0NAl) = (lambda_(K^(+))^(0) + lambda_(I^(-))^(0)) - (lambda_(Na^(+))^(0) + lambda_(I^(-))^(0))`
`= lambda_(K^(+))^(0) - lambda_(Na^(+))^(0) = 150.3- 126.9 = 23.4`
Thus the difference in `wedge_(0)` valuesfor `K^(+)` and `Na^(+)` saltsis constant and is independentof the nature of other ANIONS.
This provesthe validity of Kohlrausch's law.


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