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If you have a bunch of them, and they weren't very expensive I would start testing in the afternoon once per day starting the day AF ends and stop as soon as you get a positive. You will usually ovulate the day after your first positive OPK. This is why temping is handy with OPKs. The OPKs can predict when you will ovulate, temping will ensure that you did. If your cycle is usually pretty regular or after you've used the OPKs for a awhile and you notice you typically O around the same cycle day per month you can start testing with OPKs closer to your "normal" O day. Some women test multiple times throughout the day and for multiple days after their first positive OPK, you have to try them and tweak the way you do it to see what works best for you to catch your surge. GL
I would test more than once per day if it is your first time, because if you are like me, I had a negative in the afternoon but it was just barely visible, and usually I have stark white in the afternoon (faint line every morning), so I was impatient and tested again in the late evening (9pm) and it was positive. It was positive at 9am the next day and then negative again at 1pm and never went back to positive. I ovulated three days after that first positive. I would have definitely missed it if I was only testing in the afternoon. I stick to testing twice a day starting on cd9 or 10 and then when it is a little darker I start testing three times per day. This time my surge was much longer than last cycle, at least two full days of positives.