Does the time of Fajr (dawn) prayer start after the first Athaan (call for prayer), or the second one?
All perfect praise be to Allah,The Lord of The Worlds The time of Fajr prayer starts after the second Adhan. And Allah Knows Best.
Should nail polish be removed before making ablution?
Yes, it should be removed because it prevents water from reaching the nails.
Is it permissible to pay the Zakah (obligatory charity) for settling the debt of a deceased relative?
It is impermissible to pay the Zakah for settling the debt of the deceased since Zakah is paid to eligible recipients who are alive. As for the debts of the deceased, they are to be settled from the estate before dividing it amongst the heirs, but if the deceased didn`t leave an estate, then it is desirable for his/her heirs to settle those debts if they can afford them. And Allah Knows Best.
Is it permissible to make ablution without answering the call of nature after waking up?
Washing front and back openings (Istinjaa`) is not a condition for the validity of ablution because it is done to remove Najaasah (impurity), thus if there is no Najaasah, there is no need for that, and then it is permissible to make ablution without answering the call of nature. However, prayer is invalidated if there is Najaasah on the anus ,or the front opening, so it (Najaasah) must be removed for the prayer to become valid, and not the ablution.