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.
What is the ruling on performing voluntary prayers during official working hours?
All perfect praise be to Allah, The Lord of The Worlds, and may His Peace and Blessings be upon our Prophet Muhammad and upon all of his family and companions
There is no harm if there was break time during official working hours, but if not then it is impermissible. And Allah Knows Best.
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.
What is the ruling on giving Zakah (obligatory charity) to one`s relatives?
It is impermissible to pay Zakah to one`s origins (parents and grandparents) because providing for them is an obligation on their branches (sons and daughters) if they were poor, but it is permissible to give some of the Zakah money to relatives whose provision isn`t due on the giver of the Zakah.