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Question

A 50 mL of 0.02 M NH4OH solution is titrated with 0.02 M HCl. Find the pH of the solution when 50.1 mL of HCl is added.
Given: Kb(NH4OH)=1.8×105

A
2.65
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B
4.65
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C
10.35
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D
9.35
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Solution

The correct option is B 4.65
mmol of NH4OH=50×0.02=1
mmol of HCl=50.1×0.02=1.002

NH4OH (aq)+HCl (aq)NH4Cl (aq)+H2O (l)Initially: 1 1.002 0 0Final: 0 0.002 1 1
Final Concentration =Moles Total Volume
Taking Total volume 100 mL for calculation purposes.
[HCl]=0.002100=2×105 M[NH4Cl]=1100=0.01 M
We will take H+ from both HCl and hydrolysis of NH4Cl
NH4Cl will further hydrolyse as

NH+4 (aq)+H2O (l)NH4OH (aq)+H+ (aq)Equilibrium: C(1h) Ch Ch
where h is the degree of hydrolysis:
h=KwKb×Ch=10141.8×105×0.01h=5.55×108h=2.35×104
[H+]=Ch=0.01×2.35×104[H+]=2.35×106
[H+]total=[H+]HCl+[H+]NH4Cl[H+]total=(2×105)+(2.35×106)=2.235×105pH=log[H+]pH=log(2.235×105)=(50.35)pH=4.65

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