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JEE Advanced 2023 Paper 2 · Chemistry · Ionic Equilibrium · medium

55.0 mL of 0.200 M aqueous NH3 (Kb=1.00×10^-5 at 298 K) is mixed with 50.0 mL of 0.200 M HCl and the resulting solution is diluted with water to 1.00…

Numerical answer

55.0 mL55.0\ \mathrm{mL} of 0.200 M0.200\ \mathrm{M} aqueous NH3\mathrm{NH_3} (Kb=1.00×10−5K_b=1.00\times10^{-5} at 298 K298\ \mathrm{K}) is mixed with 50.0 mL50.0\ \mathrm{mL} of 0.200 M0.200\ \mathrm{M} HCl\mathrm{HCl} and the resulting solution is diluted with water to 1.00 L1.00\ \mathrm{L}. Neglect the contribution of water autoionisation to [OH−][\mathrm{OH^-}] in the buffer. What is the pH of the final solution at 298 K298\ \mathrm{K} (take Kw=1.00×10−14K_w=1.00\times10^{-14})?
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Answer: 8

Moles of NH3=55.0×0.200=11.0 mmol\mathrm{NH_3}=55.0\times0.200=11.0\ \mathrm{mmol} and moles of HCl=50.0×0.200=10.0 mmol\mathrm{HCl}=50.0\times0.200=10.0\ \mathrm{mmol}. The strong acid converts 10.0 mmol10.0\ \mathrm{mmol} of NH3\mathrm{NH_3} into NH4+\mathrm{NH_4^+}, leaving 1.0 mmol1.0\ \mathrm{mmol} NH3\mathrm{NH_3} and 10.0 mmol10.0\ \mathrm{mmol} NH4+\mathrm{NH_4^+}, a basic buffer. Dilution to 1.00 L1.00\ \mathrm{L} changes both concentrations by the same factor ([NH3]=1.0×10−3 M[\mathrm{NH_3}]=1.0\times10^{-3}\ \mathrm{M}, [NH4+]=1.0×10−2 M[\mathrm{NH_4^+}]=1.0\times10^{-2}\ \mathrm{M}), so the ratio is unaffected. Then [OH−]=Kb[NH3][NH4+]=10−5×110=1.0×10−6 M[\mathrm{OH^-}]=K_b\dfrac{[\mathrm{NH_3}]}{[\mathrm{NH_4^+}]}=10^{-5}\times\dfrac{1}{10}=1.0\times10^{-6}\ \mathrm{M}, so pOH=6\mathrm{pOH}=6 and pH=14−6=8\mathrm{pH}=14-6=8. A solution of this kind is mildly basic; [OH−]=10−6[\mathrm{OH^-}]=10^{-6} is still large enough compared with 10−710^{-7} from water that the approximation is acceptable for the stated answer. The pH is 8.
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