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.

Is the marriage contract considered valid if concluded at home by the marriage official (Ma`zon)?

Yes, it is valid as long as it is registered at the court.

Is it permissible for a woman in her waiting period (Iddah) after her husband's death to leave her house and mix with non-Mahrams?

It is not permissible for a woman in her waiting period (Iddah) after the death of her husband to leave her house except for a necessity, such as for medical treatment, nor is she allowed to mix with non-Mahrams. A woman is not permitted to mix with anyone other than her husband or Mahrams, whether she is in her waiting period or not. However, there is no harm in accepting condolences from those who visit and responding to their inquiries about her well-being. 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.