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.
Does Istigfar (Asking Allah for forgiveness) between the first and the second part of Friday prayer`s sermon render the prayer invalid?
Talking during Friday prayer`s sermon is disliked, but there is no harm in offering Istigfar between the two parts of the sermon, and it doesn`t invalidate the prayer as it is actually from Sunnah. 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.
If husband doesn`t pray, but wife does, is their marriage contract considered valid or not?
All perfect praise be to Allah the Lord of the Worlds. May Allah`s peace and blessings be upon our Prophet Mohammad and upon all his family and companions.
Not observing daily prayers is a grave sin, but doesn`t invalidate a person`s marriage contract. However, we advise you to save your husband from hellfire by convincing him to observe the prescribed prayers. And Allah The Almighty Knows Best.