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 woman`s face an Awrah (a private part) that should be covered?

During prayer, a woman`s whole body is a private part except the hands and the face. Outside the time of prayer, scholars are of the view that a woman should wear on her Islamic attire to avoid temptation.

Is the one who gives up on marriage because he can`t afford it considered sinful?

Marriage is desirable, but one who can`t afford it isn`t considered sinful. However, he should supplicate to Allah, and seek His forgiveness.

What is the ruling on loudly sending prayers on the Prophet (PBUH ) after the call for prayer Athaan?

All perfect praise be to Allah, The Lord of The Worlds                                                                                                                                                            Sending prayers on the Prophet after Athaan is a Sunnah for the Mou`zen (caller for prayer ) and the hearer. However, there is no harm in doing it loudly after the end of Athaan, but sometimes, it shouldn`t so that people wouldn`t think that it is an integral part of the Athaan. And Allah Knows Best.