Is it permissible to pray with a heater (stove) in front of me?
There is no harm in praying with a heater in front of you, as long as you do not intend to venerate the fire or imitate those who worship it. And Allah Knows Best.
Is it permissible to pay the expiation of an oath to a charitable party as it feeds the poor and needy such as Tkiyet Um Ali?
There is no harm on authorizing someone to handle the expiation of another to the poor and needy, since Shafiee's jurists stated that authorizing someone for the purpose of distributing Zakah, expiation and vow is permissible as stated in [Mughni Al-Muhtajj,vol.3/pp.237]. At last, the intention of the person who intends to authorize someone else suffices in this regard. 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.