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I have been noticing that sometimes when referring to ownership, the preposition to is frequently more accurate than of. For example, consider the phrase "These are the keys to the door," and "These are the keys of the door." Is there any pattern to clearly differentiate when to use one over the other?

Or, for example, "I am new to this store." In this case, can I use another preposition other than to?

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What you are considering here are established expressions, such as new to... and keys to....

Whether you use these prepositions or others depends on the context. While these can be the keys to the door, they can also be the keys of the kingdom or the keys in the drawer.

And while you can be new to the store, you can also be new in this department, new around the block, new under our roof, new for the purposes of... and so on.

The context is everything.

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