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 guardian (Big brother) to unlawfully stop his sister from getting married?
If the guardian denies her right in getting married for an unlawful reason, she should go to court in order to settle that matter, and the guardian is considered sinful in this case.
Is it permissible for the young woman to turn the suitor down if she had no feelings for him?
Yes, it is permissible for her to do so.
When is supplication (du‘a) more likely to be accepted: before or after breaking the fast in Ramadan?
Du‘a is accepted at all times, and this is part of Allah’s mercy and generosity toward His servants.
The Prophet ﷺ said: "No Muslim makes a supplication that does not involve sin or severing family ties except that Allah grants them one of three things: either He grants their supplication immediately, or He stores it for them in the Hereafter, or He averts from them an equivalent harm." [Narrated by Ahmad]
However, in Ramadan, du‘a is especially likely to be accepted shortly before breaking the fast.
The Prophet ﷺ said: "Three supplications are never rejected: the supplication of a fasting person until they break their fast, the supplication of a just leader, and the supplication of an oppressed person. Allah raises it above the clouds, opens the gates of heaven for it, and says: ‘By My might, I will surely grant you victory, even if after a while.’" [Narrated by Al-Tirmidhi]