Is it permissible for a woman to shake hands with her brother-in-law?

It is forbidden for the woman to shake hands with her brother-in-law because he isn`t a Mahram (unmarriageable) of hers.

Is prayer mandatory on a dying person who goes through a state of unconsciousness, then wakes up?

If he wakes up and was conscious, then he should pray the way/manner he could, but if he wasn't, then he is exempted from obligatory prayer as Allah Says in this regard (What means): "On no soul doth God Place a burden greater than it can bear." [Al-Baqarah/286].

Is it permissible for a person, who vowed to offer two Rak`ahs (units of prayer) everyday for Allah`s sake, to do so after the Fajr (dawn) prayer?

In principle, a vow should be fulfilled as it was originally intended, and if its time lapses then, it should be fulfilled at any time because of the vow. Therefore, it is permissible to offer them after the Fajr prayer, and there is no prohibition in doing so. However, it is preferable for him to offer these two Rak`ahs at some other time to avoid the disagreement amongst the scholars in this regard.

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.