Is it permissible for someone to make a supplication to Allah to marry an already married, or an engaged woman?
No, it isn`t, and the person who does so is sinful before Allah, The Almighty.
Is Zakah due on the orphan`s money?
Yes, Zakah is due on the money of the orphan.
Someone asked me to pay off his debt on his behalf as a loan, without any compensation. When I went to the creditor, he told me that if I paid the full amount at once, rather than in installments, he would give me a certain discount. Is this permissible? And if he applies the discount, to whom does the deducted amount belong?
If part of the debt is paid and the creditor forgives the remaining amount, the waiver is valid, and the remaining debt is no longer the responsibility of the original debtor. The person who paid the debt on behalf of another has no right to claim any portion of the original debt. And Allah Knows Best.
What is the ruling on a man leading his sisters in obligatory prayer, or Taraweeh prayer (Night prayer in Ramadan)?
The prayer of the man who leads his wife, or sisters in prayer is valid, but it is more rewarding for him to offer obligatory prayer in the mosque. And Allah Knows Best.