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.
Can someone who begins a voluntary fast break it?
It is preferable for someone who begins an act of worship not to break it.
Allah the Exalted has said {what means}: "and let not your [good] deeds come to nought!" [Muhammad/33].
However, if a person starts a voluntary fast (nafl) and needs to break it, they are going against what is preferable, but there is no sin upon them.
Does smoking break the fast?
Yes, smoking breaks the fast because smoke particles intentionally enter the lungs, which are considered part of the body cavity (jauf).
When is supplication (du‘a) more likely to be accepted: before or after breaking the fast in Ramadan?
Du‘a is accepted at all times, and this is part of Allah’s mercy and generosity toward His servants.
The Prophet ﷺ said: "No Muslim makes a supplication that does not involve sin or severing family ties except that Allah grants them one of three things: either He grants their supplication immediately, or He stores it for them in the Hereafter, or He averts from them an equivalent harm." [Narrated by Ahmad]
However, in Ramadan, du‘a is especially likely to be accepted shortly before breaking the fast.
The Prophet ﷺ said: "Three supplications are never rejected: the supplication of a fasting person until they break their fast, the supplication of a just leader, and the supplication of an oppressed person. Allah raises it above the clouds, opens the gates of heaven for it, and says: ‘By My might, I will surely grant you victory, even if after a while.’" [Narrated by Al-Tirmidhi]