The first sentence can be translated literally as:
“I work from Monday to Friday.”
In the second sentence, it helps to think that ‘fica’ means ‘is situated’. This then makes better sense of the use of ‘a’: A clumsy but literal translation would be:
“The airport is situated at 5 km from my house”
But of course in English we would simply say:
“The airport is 5km from my house.”