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Exercises · 6.44

Q.The ionization constant of phenol is 1.0 × 10⁻¹⁰. What is the concentration of phenolate ion in 0.05 M solution of phenol? What will be its degree of ionization if the solution is also 0.01M in sodium phenolate?

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For a weak acid (phenol, Ka=1.0×10−10K_a = 1.0 \times 10^{-10}) in 0.05 M solution, the phenolate ion concentration is 7.07×10−67.07 \times 10^{-6} M. When 0.01 M sodium phenolate is added, the common ion effect suppresses ionization, giving a degree of ionization of 1.0×10−81.0 \times 10^{-8}.

This problem is a classic weak acid ionization, but with a twist: the second part introduces the common ion effect. Let’s start with the core concept.

Phenol (C6H5OHC_6H_5OH) is a weak acid. It partially dissociates in water:

C6H5OH⇌C6H5O−+H+C_6H_5OH \rightleftharpoons C_6H_5O^- + H^+

The ionization constant KaK_a is given as 1.0×10−101.0 \times 10^{-10}. This tiny number tells us the equilibrium lies far to the left — very few molecules actually ionize. The phenolate ion (C6H5O−C_6H_5O^-) is the conjugate base.

For the first part, we need the concentration of phenolate ion in a pure 0.05 M solution. For the second part, we add sodium phenolate, a salt that fully dissociates to give C6H5O−C_6H_5O^- ions. This common ion (phenolate) shifts the equilibrium left, suppressing further ionization — that’s the common ion effect. The degree of ionization (α\alpha) will drop dramatically.

Let’s work through it step by step.

  1. Set up the equilibrium for pure phenol. Let initial concentration of phenol be c=0.05c = 0.05 M. Let xx be the concentration of C6H5O−C_6H_5O^- (and also H+H^+) at equilibrium.

C6H5OH⇌C6H5O−+H+C_6H_5OH \rightleftharpoons C_6H_5O^- + H^+

Initial: 0.050.05 M, 00, 00

Change: −x-x, +x+x, +x+x

Equilibrium: 0.05−x0.05 - x, xx, xx

The KaK_a expression is:

Ka=[C6H5O−][H+][C6H5OH]=x⋅x0.05−x=1.0×10−10K_a = \frac{[C_6H_5O^-][H^+]}{[C_6H_5OH]} = \frac{x \cdot x}{0.05 - x} = 1.0 \times 10^{-10}

  1. Solve for xx using the weak acid approximation. Since KaK_a is very small, xx will be tiny compared to 0.05. So we can approximate 0.05−x≈0.050.05 - x \approx 0.05. This is valid if x<5%x < 5\% of 0.05 — we’ll check later.

x2=(1.0×10−10)×0.05=5.0×10−12x^2 = (1.0 \times 10^{-10}) \times 0.05 = 5.0 \times 10^{-12}

x=5.0×10−12=5×10−6≈2.236×10−6 Mx = \sqrt{5.0 \times 10^{-12}} = \sqrt{5} \times 10^{-6} \approx 2.236 \times 10^{-6} \text{ M}

Watch out

A common mistake is to forget the square root. Also, always check the approximation: x/0.05=(2.236×10−6)/0.05=4.47×10−5x / 0.05 = (2.236 \times 10^{-6}) / 0.05 = 4.47 \times 10^{-5}, which is 0.0045% — far less than 5%, so the approximation is excellent.

So the concentration of phenolate ion in pure 0.05 M phenol is [C6H5O−]=x=2.236×10−6[C_6H_5O^-] = x = 2.236 \times 10^{-6} M. Since the ionization is 1:1, [C6H5O−]=[H+]=Kac=5×10−12=2.24×10−6[C_6H_5O^-] = [H^+] = \sqrt{K_a c} = \sqrt{5 \times 10^{-12}} = 2.24 \times 10^{-6} M — the answer to the first part.

Tip

For a weak acid HA, [A−]=[H+]=Kac[A^-] = [H^+] = \sqrt{K_a c} when no other source of ions is present. This is a direct formula worth remembering.

  1. Now the second part: solution also 0.01 M in sodium phenolate. Sodium phenolate (C6H5ONaC_6H_5ONa) is a strong electrolyte — it dissociates completely:

C6H5ONa→C6H5O−+Na+C_6H_5ONa \rightarrow C_6H_5O^- + Na^+

So initially, we have 0.01 M phenolate ions from the salt, plus the phenol at 0.05 M. Let’s set up the new equilibrium. Let yy be the concentration of phenol that ionizes (i.e., the additional C6H5O−C_6H_5O^- and H+H^+ produced). But note: the initial phenolate from salt is 0.01 M, so at equilibrium:

[C6H5O−]=0.01+y[C_6H_5O^-] = 0.01 + y

[H+]=y[H^+] = y

[C6H5OH]=0.05−y[C_6H_5OH] = 0.05 - y

The KaK_a expression:

Ka=(0.01+y)⋅y0.05−y=1.0×10−10K_a = \frac{(0.01 + y) \cdot y}{0.05 - y} = 1.0 \times 10^{-10}

  1. Apply the common ion effect approximation. …

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