An 80mm fan will line up perfectly and should blow out.
There are two rules of thumb to consider with fan placement.
1. When possible, you should have equal air flow into and out of the case. If you do not have this, you run into issues with positive and negative pressure in the case. Depending on your application, you may or may not want either of these situations. e.g. more intake results in positive pressue in the case which (if you have filters on your fans) keeps dust out.
2. Intakes should blow into the bottom of case and exhausts blow air out of the top of the case. This is simply to take advantage of the fact that heat rises.