​Which of the following mixtures can not act as buffer solution ? 

1
NaOH + CH3COOH (1 : 1 mole ratio)
2
NH4OH + HCl (2 : 1 mole ratio)
3
CH3COOH + NaOH (2 : 1 mole ratio) 
4
CH3COOH + NaOH (3 : 2 mole ratio)

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