What is the plural form of ‘that’ when it is used as a relative pronoun and when as a demonstrative pronoun respectively?

He became rich overnight. What part of speech is 'overnight'?

The nightingale is a singing bird. In this singing is a/an --

I Came home after the rain -----.

The Doctor took the round in the hospital. Here 'round' is a/an ---

Alumni is the plural from of