Amphoteric = acid and base, so you should be able to consider whether a compound could act either way... Can it pick up/donate electrons (Lewis defintion)? Can it pick up/donate H+ (Bronstead Lowrey definition)?
The most common examples I can think of are water (obviously) and amino acids. You should definitely know those.
NaHCO3 is amphoteric because it will dissociate into Na+ and HCO3-. HCO3- can act as a base by picking up a proton or it can donate its H to form carbonate.
I guess the only way to really tell weather a substance is amphoteric is to see which reactions it can undergo.
NaHCO3 will become Na+ and HCO3-. The HCO3- can donate H+ which will make NaHCO3 act as an acid. The HCO3- can also accept an H+ making H2CO3, and NaHCO3 will then act as a base.
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