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Example · Example 18

Q.Explain, with reference to the ionic-interaction picture, why the molar conductivity of a strong electrolyte such as KCl\text{KCl} increases only gradually on dilution and extrapolates smoothly to Λm0\Lambda_m^{0} at infinite dilution, whereas that of a weak electrolyte such as CH3COOH\text{CH}_3\text{COOH} rises steeply near infinite dilution and cannot be obtained by extrapolation.

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A strong electrolyte like KCl\text{KCl} is essentially completely ionized at every concentration at which it is normally studied. At higher concentrations, the ions are close together and their motion under an applied field is somewhat hindered by inter-ionic electrostatic attraction (each ion is surrounded by a loose 'ionic atmosphere' of opposite charge that drags against its motion). On dilution, ions move further apart, this retarding effect weakens, ionic mobility rises, and so Λm\Lambda_m increases — but only gradually, because the number of ions per mole was already essentially fixed (complete dissociation) at all concentrations; only their mobility was changing. This gradual, well-behaved variation extrapolates smoothly to a finite limiting value Λm0\Lambda_m^{0} as C→0C\to0. A weak electrolyte like CH3COOH\text{CH}_3\text{COOH}, by contrast, is only partially dissociated, and its degree of dissociation α\alpha itself rises sharply as the solution is diluted (by Le Chatelier's principle applied to the dissociation equilibrium — diluting favours the side with more particles, i.e. more ions). So on dilution, both the number of ions present and their mobility increase, and the number-of-ions effect dominates and grows very sharply as C→0C\to0 (approaching α→1\alpha\to1, ful …

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