Heat loss increases with increasing water temperature so to minimize heat loss and thus cost, you would only want to heat the pool when you use it. Unfortunately, that is not always practical because it takes time to heat the pool. If you are using the pool nearly every day then you are probably doing the right thing by heating during the day since heat loss tends to increase during the night due to dropping dew points and temperatures but since you are using a cover and don't lose much heat it probably doesn't matter much either way.
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