Which of the following pairs constitutes a buffer?

One litre buffer solution was prepared by adding $0.10 \ mol$ each of $NH_3$ and $NH_4Cl$ in deionised water. The change in $pH$ on addition of $0.05 \ mol$ of $HCl$ to the above solution is $............ \times 10^{-2}$ ($Nearest$ $integer$) ($Given$: $pK_b$ of $NH_3 = 4.745$ and $\log_{10} 3 = 0.477$)

The $K_a$ of $CH_3COOH$ is $1.8 \times 10^{-5}$. How many grams of $CH_3COONa$ are required in $0.1 \ M \ CH_3COOH$ to form a solution having $pH = 4.0$? (Molecular mass of $CH_3COONa = 82 \ g \ mol^{-1}$)

$3 \; g$ of acetic acid is added to $250 \; mL$ of $0.1 \; M \; HCl$ and the solution is made up to $500 \; mL$. To $20 \; mL$ of this solution,$\frac{1}{2} \; mL$ of $5 \; M \; NaOH$ is added. The $pH$ of the solution is: [Given: $pK_{a}$ of acetic acid $= 4.75$,molar mass of acetic acid $= 60 \; g/mol$,$\log 3 = 0.4771$]. Neglect any changes in volume.

Out of the following,which pair of solutions is not a buffer solution?

Calculate $pH$ of the solution obtained by mixing $50 \ mL$ of $0.2 \ M$ $NH_4Cl$ solution and $75 \ mL$ of $0.1 \ M$ $NaOH$ solution. Given $pK_b$ for aqueous $NH_3$ is $4.74$.