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Electrolyte Solutions and the Debye-Huckel Limiting Law

Ions in solution do not behave independently because each one gathers an atmosphere of opposite charge around it. That atmosphere lowers the effective concentration, and the limiting law predicts by how much.

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What a learner can do afterwards

  • Calculates ionic strength for a mixed electrolyte and explains why charge is squared in it
  • Applies the limiting law to obtain a mean activity coefficient and states its range of validity
  • Explains why a measured pH drifts from the calculated value as salt is added
  • Says why single-ion activities cannot be measured and what is quoted instead

1 · Read

Ions in solution gather a cloud of opposite charge, the ionic atmosphere, which shields each ion. Ionic strength measures how crowded that world is: halve the sum of concentration times charge squared. Charge enters squared, so one doubly charged ion counts four times as much as a singly charged one.

Try it together

Take 0.10 M sodium chloride. Sodium is plus 1 and chloride is minus 1, so I is half of 0.10 times 1 plus 0.10 times 1, which is 0.10 M. For 0.10 M magnesium sulphate, both charges are 2, so I is half of 0.10 times 4 plus 0.10 times 4, which is 0.40 M.

The Debye Huckel limiting law predicts the mean activity coefficient from the ionic strength, but it holds only in very dilute solutions. Extra salt reshapes every ion cloud, so a measured pH drifts from the ideal calculation even when no acid or base was added.

Good to know

No experiment can isolate one ion type, so single-ion activities cannot be measured. Tables quote mean coefficients for the whole salt instead. Whenever you quote a coefficient, name the salt, never the lone ion.

Charge squared sets the strength, the cloud lowers the activity, and only whole-salt means ever reach print.

2 · Watch

Take it off screen

Print a worksheetA4 with an answer key page for grown-ups. No screen, no internet.

Where it sits

Then practise

8 questions wait behind this lesson, each with its answer explained. Every answer feeds the sky: stars light as they are learned, and dim when it is time to come back.

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Electrolyte Solutions and the Debye-Huckel Limiting Law · Science, ages 20 to 22 · LightMySky