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.

Should the Zakah(obligatory charity) giver tell the poor recipient that this is the Zakah of his money?

No, he shouldn`t. But, the Zakah giver should make an intention in his heart that it is the Zakah of his money when he gives it to the poor.

Is it permissible for the guardian to give Sadaqa( voluntary charity )from the money of the orphans?

It is impermissible for the guardian to donate from the money of the orphans because he is entrusted with the safekeeping of that money, and is prohibited from donating it.

What is the ruling on a woman shaking hands with the brothers of her husband`s father, and not putting on Islamic wear before them?

The aforesaid are strangers to the their brother`s son`s wife, therefore, it is forbidden for her to take off her Islamic wear before them, or to shake hands with them.