Consider the following gas phase dissociation, PCl$_5$(g) $\rightleftharpoons$ PCl$_3$(g) + Cl$_2$(g) with equilibrium constant K$_p$ at a particular temperature and at pressure P. The degree of dissociation ($\alpha$) for PCl$_5$(g) is
PCl$_5$(g) $\rightleftharpoons$ PCl$_3$(g) + Cl$_2$(g)
$\alpha = \left(\frac{K_p}{K_p+P}\right)^{1/3}$
Let the initial moles of PCl5 be 1 and the degree of dissociation be α. We can set up an ICE table based on moles:
| Reaction: | PCl5(g) | ⇌ | PCl3(g) | + | Cl2(g) | ||
|---|---|---|---|---|---|---|---|
| Initial (mol): | 1 | 0 | 0 | ||||
| Change (mol): | -α | +α | +α | ||||
| Equil. (mol): | 1-α | α | α |
Total moles at equilibrium = (1-α) + α + α = 1+α.
The total pressure at equilibrium is given as P. Now, calculate the partial pressures using pi = Xi × Ptotal, where Xi is the mole fraction. pPCl5 = ( (1-α) / (1+α) ) P
pPCl3 = ( α / (1+α) ) P
pCl2 = ( α / (1+α) ) P The expression for the equilibrium constant Kp is:
Kp = (pPCl3 × pCl2) / pPCl5 Substitute the partial pressures:
Kp = (( αP / (1+α) ) ( αP / (1+α) )) / (( (1-α)P ) / (1+α) ) Kp = (α2P2 / (1+α)2) / (( (1-α)P ) / (1+α) ) Kp
= (α2P2 / (1+α)2) × ((1+α) / ((1-α)P)) Kp = (α2P) / ((1+α)(1-α)) Kp = (α2P) / (1-α2)
Now, rearrange to solve for α:
Kp (1-α2) = α2 P Kp - Kp α2 = α2 P Kp
= α2 P + Kp α2 Kp = α2 (P + Kp) α2
= Kp / (P + Kp) α = √( Kp / (Kp + P) ) = ( Kp / (Kp + P) )1/2
This corresponds to option (C).
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