Is Zakah due on the orphan`s money?
Yes, Zakah is due on the money of the orphan.
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 for the big brother to force his sisters to wear Hijjab (Islamic wear) if their father didn`t do his part in this regard ?
All Perfect Praise is due to Allah, The Lord of The Worlds
The father`s attention should be drawn gently and politely, and the sisters should also be reminded with good words since Allah, The Almighty, Says (What means): "O ye who believe! Save yourselves and your families from a Fire whose fuel is Men and Stones." [Al-Tahreem/6]. And Allah Knows Best.
How should I be kind to my atheist father?
Allah, The Exalted, has decreed and ordained his slaves to be kind with parents, even if they are polytheists, by honoring and obeying them in all that isn`t sinful, so that they might love Islam and embrace it as a result.