The way is works is you ask her if she'll be available and if she is then you pay her regular rate for up to 40 hrs per week and OT beyond that. But you have no guarantee that she will be free as you are no longer reserving her time for those hours.
Option A: pay for part-time hours and have multiple layers of backup plans (grandma, other sitters, SAH parent down the street) for sick kid, snow delays/cancellations, teacher work days, random holidays, half days, etc.
Option B: pay for part-time hours and plan to take time off when nanny is not free
Option C: pay for some hours DC is in school (e.g., all day on Mondays and Fridays, which are the most common for scheduled days off and afternoons-only Tues-Thurs), and plan to take off if nanny is not free during Tues-Thurs
Option D: pay for full-time hours (usually people would look for something else nanny can do during that time such as groceries, cooking, family laundry, dog-walking, depending on what nanny is willing to take on) and know that you have coverage unless nanny is ill.