As long as the pump head will push up over the wall, you should be fine. Flow thru the pipe up over the wall will either push the air on over, or flow thru/under it. If it flows under, the flow may eventually break up the air pocket into bubbles and carry them off to some other high point in the system, hopefully the expansion tank and vent. You could also put a "T" with a valve to help bleed air from these high points when needed. If the expansion tank is vented to the atmosphere, expansion tank placement will need to be such that the path of least resistance from pump outlet back to pump inlet, is thru the line comming back over the wall, and not out thru the top of the expansion tank:)
Mixing in chemicals can be done with a "T" fitting and 2 valves on the pump inlet. One valve is on the main line before both the "T" and the pump inlet. The other valve is on the open leg of the "T".. You place a container like a funnel above this second valve, and to this you add your chemicals. With the pump running, slowly close/throttle the upstream valve, and open the valve running up to the funnel/chemical container. The restriction upstream will lower the pressure at the pump inlet and force the pump to draw fluid from the container. Depending on valve position, and if the pump is running or not, you will be able to move system fluid into or out of the container/funnel to help mix/flush/clean the container.