What is the ruling on having brotherly ties between a strange man and a strange woman, and is the former considered a Mahram (unmarriageable) to the latter?

Such a relation between a strange man and a strange woman is forbidden in Islam because it involves forbidding what Allah has allowed by marriage, and allowing what Allah has forbidden such as looking and the like. Such a relation doesn`t render any act lawful between them, thus they are forbidden to look at each other, have a Khulwah (seclusion), and travel together.

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 a wife considered sinful if she asked for divorce because her husband married another woman?

A second marriage is lawful, and so it is impermissible for you to ask for divorce because of that. If you are certain that you won`t be able to deliver Allah`s rights and those of your husband`s , then it is permissible for you to ask for Khul`a (Divorce on the demand of the wife). However, you should exercise patience since after difficulties, there is easiness by the will of Allah.

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.