Consider the expressions $$a + (2\times b)$$ and $$(a\times b) + 3$$ and suppose you were asked to show that these are not equivalent arithmetically. You can put in $2$ for $a$ and $3$ for $b$ and find that the first expression has the value $2+(2\times 3) = 8$ while the second has $(2\times 3) + 3 = 9$. Then you can conclude that they are not equivalent, because equivalent expressions always have the same value no matter what you put in for the variables.
But suppose you also noticed that if you put in $1$ for $a$ and $2$ for $b$ then both expressions have the value $5$. "Why are the equivalent in one case and not in the other", you ask?
They are still not equivalent; they just happen to have the same value when you put in $1$ for $a$ and $2$ for $b$. Equivalent expressions always have the same value, and these sometimes don't, so these are not equivalent.
Or consider this analogy. Suppose you know that $A$ and $B$ are people, perhaps the same and perhaps different; you don't know who they are. But you know that $A$ had five dollars in his wallet on January 3rd while $B$ had only three dollars that day. Then you can be sure they are different people, because if they were the same person they would have had the same amount of money. But $A$ and $B$ can still be different people even if you also know that they happened to be carrying the same amount of money on a different day.