Toppling occurs when a block's center of mass is not directly above its contact area with a horizontal surface. If the center of gravity shifts to the side of the contact area, the block will begin to rotate and potentially fall over. Friction is not necessary for toppling to occur, as the block will topple due to gravitational torque acting on it. The discussion clarifies that the center of gravity must be above or to the side of the contact area for toppling to happen, not below it. Understanding these principles is crucial for analyzing stability in physical systems.