"Qual" is used in questios such as "qual sua cor favorita?" (whats is your favorite colour?). "Que" have a lot of means, can be seen as adjetive pronoun(Que show maravilhoso! means What a wonderful show!) also is a noun and preposition. In general, "qual" is used in questions but with the "que" depends of the context. Hope thats help!
Qual literally means "which" but can also be used as "what" and "O que" means "what" I think an easy way to know when to use one or another is to always view "qual" as "which"
"Which of those jackets is yours?" (Qual daqueles casacos é teu?) "What is your favorite color?" ("Qual é a tua cor favorita?") - here you can change the order of the words and say "which color is your favorite?"
If you have "What is going on?" you say "O que se está a passar?" , saying "which is going on" makes no sense whatsoever.
I'm not sure if there are any exceptions but I can't think of any right now, so I'm sure that in almost every case this rule can be applied :)
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