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 the prayer of a woman who is led by an Imam via T.V. permissible?
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. Amongst the conditions for the validity of prayer is that both the Imam and those led by him must be in the same place. Thus, the prayer of the person who is being led by a televised Imam is invalid unless he/she was with him in the same mosque. And Allah Knows Best.
What is the ruling on swearing on the Holy Quran and breaking that oath?
It is impermissible to swear on the Holy Quran in vain, and it is also impermissible to subject it to such an act since breaking the oath after swearing on the Quran entails an expiation.
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.