Does the time of Fajr (dawn) prayer start after the first Athaan (call for prayer), or the second one?
All perfect praise be to Allah,The Lord of The Worlds The time of Fajr prayer starts after the second Adhan. And Allah Knows Best.
Is it permissible for a woman to uncover her face while performing Umrah (minor Hajj)?
The woman while in a state of Ihram (ritual consecration) is obligated to uncover her face and hands, but at the same time permitted to let her head-covering garment drape from her head down over her face when non-Mahram (i.e., marriageable) men pass by her. And Allah Knows Best.
Can Zakah or Zakat al-Fitr be given to a poor brother?
Yes, it is allowed to give Zakah or Zakat al-Fitr to a poor brother, as he is considered among the eligible recipients.
Can someone who begins a voluntary fast break it?
It is preferable for someone who begins an act of worship not to break it.
Allah the Exalted has said {what means}: "and let not your [good] deeds come to nought!" [Muhammad/33].
However, if a person starts a voluntary fast (nafl) and needs to break it, they are going against what is preferable, but there is no sin upon them.