When I got my CO2 system w/pH controller from Greenleaf, Orlando told me to measue the pH first then set the controller for 1 degree less pH as a starting point. Then fine tune it by watch the drop checker. I would assume that you could also look at the fish and plants. I found this worked for me and I have slightly adjusted it from that start point. I also leave everything running at night so that there is a steady supplie of CO2 in the water when the lights come on in the morning.
Hope this helps. Congrats on getting a CO2 system.
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