Which of the following buffer solutions will have the highest acidic character?

In a buffer solution,the ratio of $NH_4Cl$ to $NH_4OH$ is $1:1$. If this ratio is changed to $2:1$,the $pH$ value of the buffer will ...

$A$ buffer solution of $100 \ mL$ has a $pH$ value of $4$. When $1 \ mL$ of dilute $HCl$ is added to it,what happens to the $pH$ of the buffer solution?

$20 \ mL$ of $0.1 \ (N)$ acetic acid is mixed with $10 \ mL$ of $0.1 \ (N)$ solution of $NaOH$. The $pH$ of the resulting solution is ($pK_a$ of acetic acid is $4.74$). (in $.74$)

The $pH$ of the solution containing $50 \ mL$ each of $0.10 \ M$ sodium acetate and $0.01 \ M$ acetic acid is $.......$
[Given $pK_{a}$ of $CH_{3}COOH = 4.57$] (in $.57$)

Which of the following cannot act as a buffer solution?