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NCERT Exemplar · Q31

Q.A sparingly soluble salt gets precipitated only when the product of concentration of its ions in the solution (Qsp) becomes greater than its solubility product. If the solubility of BaSO4 in water is 8 × 10^-4 mol dm^-3. Calculate its solubility in 0.01 mol dm^-3 of H2SO4.

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In pure water BaSO₄ dissolves to 8×10−48 \times 10^{-4} mol dm⁻³; in 0.01 M H₂SO₄ the common sulfate ion suppresses dissociation, reducing solubility to 6.4×10−56.4 \times 10^{-5} mol dm⁻³.


When a sparingly soluble salt like barium sulfate sits in equilibrium with its ions, the product of those ion concentrations is fixed at a constant called the solubility product, KspK_{\text{sp}}. Adding a solution that already contains one of those ions—here, sulfate from sulfuric acid—shifts the equilibrium backward (Le Chatelier), forcing less BaSO₄ to dissolve. This is the common-ion effect.

The key is to first find KspK_{\text{sp}} from the pure-water solubility, then use that same KspK_{\text{sp}} to find the new solubility when sulfate is already present.


Step-by-step solution

1. Write the dissolution equilibrium and KspK_{\text{sp}} expression.

Barium sulfate dissociates as

BaSO4(s)⇌Ba2+(aq)+SO42−(aq).\text{BaSO}_4(s) \rightleftharpoons \text{Ba}^{2+}(aq) + \text{SO}_4^{2-}(aq).

The solubility product is

Ksp=[Ba2+][SO42−].K_{\text{sp}} = [\text{Ba}^{2+}][\text{SO}_4^{2-}].

2. Calculate KspK_{\text{sp}} from the solubility in pure water.

In pure water, if the solubility is s=8×10−4s = 8 \times 10^{-4} mol dm⁻³, then at equilibrium

[Ba2+]=s=8×10−4 mol dm−3,[SO42−]=s=8×10−4 mol dm−3.[\text{Ba}^{2+}] = s = 8 \times 10^{-4} \, \text{mol dm}^{-3}, \quad [\text{SO}_4^{2-}] = s = 8 \times 10^{-4} \, \text{mol dm}^{-3}.

Hence

Ksp=(8×10−4)(8×10−4)=64×10−8=6.4×10−7.K_{\text{sp}} = (8 \times 10^{-4})(8 \times 10^{-4}) = 64 \times 10^{-8} = 6.4 \times 10^{-7}.

Ksp(BaSO4)=6.4×10−7K_{\text{sp}}(\text{BaSO}_4) = 6.4 \times 10^{-7}

3. Set up the equilibrium in 0.01 M H₂SO₄.

Sulfuric acid is a strong acid and fully dissociates (both protons in dilute solution):

H2SO4→2H++SO42−.\text{H}_2\text{SO}_4 \rightarrow 2\text{H}^+ + \text{SO}_4^{2-}.

So the initial sulfate concentration is [SO42−]0=0.01[\text{SO}_4^{2-}]_0 = 0.01 mol dm⁻³.

Let the solubility of BaSO₄ in this solution be s′s'. Then at equilibrium:

[Ba2+]=s′,[SO42−]=0.01+s′.[\text{Ba}^{2+}] = s', \quad [\text{SO}_4^{2-}] = 0.01 + s'.

4. Apply the solubility-product condition.

Since KspK_{\text{sp}} is unchanged,

Ksp=s′⋅(0.01+s′)=6.4×10−7.K_{\text{sp}} = s' \cdot (0.01 + s') = 6.4 \times 10^{-7}.

5. Make the approximation s′≪0.01s' \ll 0.01.

Because the common ion suppresses solubility, we expect s′s' to be much smaller than 0.01. Assume 0.01+s′≈0.010.01 + s' \approx 0.01: …

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