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Q.Suggest a way to determine the Λm0\Lambda^0_m value of water.

Telangana TsbieTextbookSubjective· 2mImportance★★★★★
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The limiting molar conductivity Λm0\Lambda_m^0 of water is determined indirectly using Kohlrausch’s law of independent migration of ions — by adding the Λm0\Lambda_m^0 values of its constituent ions (HX+\ce{H+} and OHX−\ce{OH-}), which are obtained from the Λm0\Lambda_m^0 of strong electrolytes like HCl\ce{HCl}, NaOH\ce{NaOH}, and NaCl\ce{NaCl}.


Why we can’t measure it directly

Water is a weak electrolyte. It dissociates only slightly:

HX2O⇌HX++OHX−\ce{H2O <=> H+ + OH-}

If you try to measure its molar conductivity directly, the concentration of ions is tiny, and the conductivity is dominated by impurities. Extrapolating to infinite dilution is impossible because the dissociation itself changes with concentration. So we need an indirect route.

The key idea is Kohlrausch’s law: at infinite dilution, each ion contributes a fixed amount to the molar conductivity, independent of the other ion it came from. That means:

Λm0(electrolyte)=ν+λ+0+ν−λ−0\Lambda_m^0(\text{electrolyte}) = \nu_+ \lambda_+^0 + \nu_- \lambda_-^0

where ν\nu are the number of ions per formula unit, and λ0\lambda^0 are the limiting ionic conductivities.

For water, we want:

Λm0(HX2O)=λ0(HX+)+λ0(OHX−)\Lambda_m^0(\ce{H2O}) = \lambda^0(\ce{H+}) + \lambda^0(\ce{OH-})

So if we can find λ0(HX+)\lambda^0(\ce{H+}) and λ0(OHX−)\lambda^0(\ce{OH-}) from known strong electrolytes, we’re done.


Step-by-step determination

1. Choose three strong electrolytes that contain HX+\ce{H+}, OHX−\ce{OH-}, and a common counterion.

A classic set is:

  • HCl\ce{HCl} — gives λ0(HX+)+λ0(ClX−)\lambda^0(\ce{H+}) + \lambda^0(\ce{Cl-})
  • NaOH\ce{NaOH} — gives λ0(NaX+)+λ0(OHX−)\lambda^0(\ce{Na+}) + \lambda^0(\ce{OH-})
  • NaCl\ce{NaCl} — gives λ0(NaX+)+λ0(ClX−)\lambda^0(\ce{Na+}) + \lambda^0(\ce{Cl-})

All three are strong electrolytes, so their Λm0\Lambda_m^0 values can be measured directly by extrapolating conductivity vs. c\sqrt{c} to zero concentration (Kohlrausch’s plot).

2. Write the three equations.

Let:

  • A=Λm0(HCl)=λ0(HX+)+λ0(ClX−)A = \Lambda_m^0(\ce{HCl}) = \lambda^0(\ce{H+}) + \lambda^0(\ce{Cl-})
  • B=Λm0(NaOH)=λ0(NaX+)+λ0(OHX−)B = \Lambda_m^0(\ce{NaOH}) = \lambda^0(\ce{Na+}) + \lambda^0(\ce{OH-})
  • C=Λm0(NaCl)=λ0(NaX+)+λ0(ClX−)C = \Lambda_m^0(\ce{NaCl}) = \lambda^0(\ce{Na+}) + \lambda^0(\ce{Cl-})

3. Combine them to isolate λ0(HX+)+λ0(OHX−)\lambda^0(\ce{H+}) + \lambda^0(\ce{OH-}).

Notice that:

A+B−C=[λ0(HX+)+λ0(ClX−)]+[λ0(NaX+)+λ0(OHX−)]−[λ0(NaX+)+λ0(ClX−)]A + B - C = [\lambda^0(\ce{H+}) + \lambda^0(\ce{Cl-})] + [\lambda^0(\ce{Na+}) + \lambda^0(\ce{OH-})] - [\lambda^0(\ce{Na+}) + \lambda^0(\ce{Cl-})]

The λ0(NaX+)\lambda^0(\ce{Na+}) and λ0(ClX−)\lambda^0(\ce{Cl-}) cancel, leaving:

A+B−C=λ0(HX+)+λ0(OHX−)A + B - C = \lambda^0(\ce{H+}) + \lambda^0(\ce{OH-})

And that sum is exactly Λm0(HX2O)\Lambda_m^0(\ce{H2O}). …

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