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Problems · Problem 6.23

Q.Determine the degree of ionization and pH of a 0.05M of ammonia solution. The ionization constant of ammonia can be taken from Table 6.7. Also, calculate the ionization constant of the conjugate acid of ammonia.

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For a weak base like ammonia, the degree of ionization (α\alpha) is found from Kb=Cα2/(1−α)K_b = C\alpha^2/(1-\alpha), and pH follows from [OH−]=Cα[OH^-] = C\alpha. Using Kb=1.77×10−5K_b = 1.77 \times 10^{-5} for 0.05 M NH₃, we get α≈0.0188\alpha \approx 0.0188, pH ≈10.95\approx 10.95, and KaK_a for NH₄⁺ is 5.65×10−105.65 \times 10^{-10}.

Why This Approach Works

Ammonia in water is a classic weak base — it doesn't fully ionize. Instead, it establishes an equilibrium:

NH3(aq)+H2O(l)⇌NH4+(aq)+OH−(aq)NH_3(aq) + H_2O(l) \rightleftharpoons NH_4^+(aq) + OH^-(aq)

The ionization constant KbK_b tells us how far this reaction goes. From Table 6.7 (NCERT), KbK_b for ammonia is 1.77×10−51.77 \times 10^{-5} at 25°C.

The degree of ionization α\alpha is the fraction of ammonia molecules that have accepted a proton. For a weak base, α\alpha is small, so we can often simplify calculations — but we'll check that assumption.

The conjugate acid of ammonia is the ammonium ion, NH₄⁺. For any conjugate acid-base pair, Ka×Kb=KwK_a \times K_b = K_w, where Kw=1.0×10−14K_w = 1.0 \times 10^{-14} at 25°C. This lets us find KaK_a for NH₄⁺ directly.

Step-by-Step Solution

1. Set up the equilibrium table

Let initial concentration of NH₃ be C=0.05C = 0.05 M. If α\alpha is the degree of ionization:

SpeciesInitial (M)Change (M)Equilibrium (M)
NH₃CC−Cα-C\alphaC(1−α)C(1-\alpha)
NH₄⁺0+Cα+C\alphaCαC\alpha
OH⁻0+Cα+C\alphaCαC\alpha

2. Write the KbK_b expression

Kb=[NH4+][OH−][NH3]=(Cα)(Cα)C(1−α)=Cα21−αK_b = \frac{[NH_4^+][OH^-]}{[NH_3]} = \frac{(C\alpha)(C\alpha)}{C(1-\alpha)} = \frac{C\alpha^2}{1-\alpha}

Substitute known values:

1.77×10−5=0.05⋅α21−α1.77 \times 10^{-5} = \frac{0.05 \cdot \alpha^2}{1-\alpha}

3. Solve for α\alpha

This is a quadratic in α\alpha. Multiply through:

1.77×10−5(1−α)=0.05α21.77 \times 10^{-5} (1-\alpha) = 0.05 \alpha^2

1.77×10−5−1.77×10−5α=0.05α21.77 \times 10^{-5} - 1.77 \times 10^{-5} \alpha = 0.05 \alpha^2

Rearrange:

0.05α2+1.77×10−5α−1.77×10−5=00.05 \alpha^2 + 1.77 \times 10^{-5} \alpha - 1.77 \times 10^{-5} = 0

Using the quadratic formula α=−b±b2−4ac2a\alpha = \frac{-b \pm \sqrt{b^2 - 4ac}}{2a} with a=0.05a = 0.05, b=1.77×10−5b = 1.77 \times 10^{-5}, c=−1.77×10−5c = -1.77 \times 10^{-5}:

α=−1.77×10−5±(1.77×10−5)2+4(0.05)(1.77×10−5)2(0.05)\alpha = \frac{-1.77 \times 10^{-5} \pm \sqrt{(1.77 \times 10^{-5})^2 + 4(0.05)(1.77 \times 10^{-5})}}{2(0.05)}

The negative root gives a negative α\alpha (impossible), so take the positive root:

α=−1.77×10−5+3.13×10−10+3.54×10−60.1\alpha = \frac{-1.77 \times 10^{-5} + \sqrt{3.13 \times 10^{-10} + 3.54 \times 10^{-6}}}{0.1}

α=−1.77×10−5+3.5403×10−60.1\alpha = \frac{-1.77 \times 10^{-5} + \sqrt{3.5403 \times 10^{-6}}}{0.1}

α=−1.77×10−5+1.8816×10−30.1\alpha = \frac{-1.77 \times 10^{-5} + 1.8816 \times 10^{-3}}{0.1}

α=1.8639×10−30.1=0.01864\alpha = \frac{1.8639 \times 10^{-3}}{0.1} = 0.01864

Tip

Since α≈0.019\alpha \approx 0.019 is much less than 0.05, we could have used the approximation 1−α≈11-\alpha \approx 1, giving α=Kb/C=1.77×10−5/0.05=3.54×10−4=0.0188\alpha = \sqrt{K_b/C} = \sqrt{1.77 \times 10^{-5} / 0.05} = \sqrt{3.54 \times 10^{-4}} = 0.0188. The exact value (0.01864) is very close — the approximation works well here.

4. Calculate [OH−][OH^-] and pOH

[OH−]=Cα=0.05×0.01864=9.32×10−4 M[OH^-] = C\alpha = 0.05 \times 0.01864 = 9.32 \times 10^{-4} \text{ M} …

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