“On top" is an expression which means:
1. At the highest point or peak.
2. In a dominant, controlling or successful position.
“On top of” is an expression meaning:
1. On or at the uppermost point or side of.
2. Informal.
a. In control of
b. Fully informed about
3. Besides; in addition to
4. Following closely upon; coming immediately after.
A good dictionary, such as the American Heritage Dictionary of the English language (if you can afford it) would answer questions such as this one.