Biological and chemical warfare! Biological weapons with the discovery of biology and chemical weapons with the discovery of chemistry. In the late game, these could be loaded into missiles.
I'm not sure how you can get civil war to work successfully - maybe cities with great people can rebel if there aren't enough city improvements corresponding to that great leader.
There could also be civil wars linked to the spread of religion - if enough of your cities don't have your state religion they could rebel.
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