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.
Who should pay the Zakah (obligatory charity) from the orphan`s money?
His/her guardian, and if the latter fails to do so, then the orphan himself/herself is obliged to pay the Zakah once he/she reaches puberty, and is capable of handling his/her own affairs. And Allah Knows Best.
My brother is settling a debt on my behalf and in return he takes 30% interest as an additional amount of the whole sum. Is this lawful or not?
This additional amount is considered prohibited interest (Riba) according to Islamic law, and it is not permissible to take it. And Allah Knows Best.
Is it permissible for a wife to give her money to her family as a charity, or a gift without asking her husband, or seeking his consent?
The wife has the right to give her money as a charity, or a gift to her family, or to other people after consulting her husband out of respect, and this is the meaning of treating on footing of kindness and equity. Therefore, if he wanted to stop her from helping her family, then there is no harm in not telling him.