"à" is used when:
* The word following it is feminine: Je vais à la librairie (the bookstore).
* The word following it is masculine and starts with a consonant sound: Je vais à l'école (school).
"au" is used when:
* The word following it is masculine and starts with a vowel sound: Je vais au cinéma (the cinema).
Why the difference?
This is a bit of a quirk of French pronunciation. "Au" is a contraction of "à le," but the "e" at the end of "le" is silent when it's followed by a vowel sound.
In summary:
* Masculine noun, vowel sound: "au"
* Masculine noun, consonant sound: "à"
* Feminine noun: "à"
Let me know if you have other examples you'd like to explore!