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 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.
What is the expiation for being forced to give a false testimony in order to achieve reform?
Achieving reform is done by following the way of Allah through giving back rights to whom they belong. Therefore, repenting to Allah from false testimony is only achieved by abrogating it, and the person in question should expiate for that oath if he had taken it, so that Allah may forgive him.
Is it permissible for a person to sever ties with his sister because her husband had quit prayer and done him harm?
A sister is a blood-relative and maintaining blood-relations is obligatory in Islam. As regards her husband, he should be invited to the way of Allah with wisdom and beautiful preaching.