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Questions 4-15 · Q4

Q.Derive the relationship between degree of dissociation of an electrolyte and van't Hoff factor.

Maharashtra MsbshseTextbookSubjectiveImportance★★★★★
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Step 1. Consider a general electrolyte AxByA_xB_y dissociating as AxBy⇌xAy++yBx−A_xB_y \rightleftharpoons xA^{y+}+yB^{x-}.

Step 2. Starting with exactly 1 mole of AxByA_xB_y dissolved, and letting α\alpha be the degree of dissociation: at equilibrium, (1−α)(1-\alpha) mol of undissociated AxByA_xB_y remains, while xαx\alpha mol of cation Ay+A^{y+} and yαy\alpha mol of anion Bx−B^{x-} have formed.

Step 3. Total moles of particles present after dissociation = (1−α)+xα+yα=1+α(x+y−1)(1-\alpha)+x\alpha+y\alpha = 1+\alpha(x+y-1). Writing n=x+yn=x+y (total ions from one formula unit on COMPLETE dissociation), this is 1+α(n−1)1+\alpha(n-1).

Step 4. By definition, i=total particles after dissociationmoles of formula units originally dissolved=1+α(n−1)1=1+α(n−1)i = \dfrac{\text{total particles after dissociation}}{\text{moles of formula units originally dissolved}} = \dfrac{1+\alpha(n-1)}{1} = 1+\alpha(n-1).

Step 5. Rearranging for alpha gives the companion relation α=i−1n−1\alpha=\dfrac{i-1}{n-1}.

✓Final answer

i = 1 + alpha(n-1), equivalently alpha = (i-1)/(n-1), where n is the total number of ions one formula unit gives on complete dissociation.

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