I took a car from the Orphans' Fund Development Institution; is there usury (Riba) involved in this transaction?

If the Sharia's conditions were met, then there is no harm in this. And Allah The Exalted Knows Best.

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 smoking?

All Perfect Praise is due to Allah, The Lord of The Worlds

Smoking is forbidden (Haram) since it is harmful to one`s health as confirmed by trustful physicians, and Islam has forbidden taking anything that causes harm. The Prophet (PBUH) said: "There should be neither harm nor reciprocated harm." [Ibn Majah and Ahmad]. And Allah Knows Best.

A pious man proposed to me and my father was hesitant in this regard because he is black, am I sinful if I accepted his proposal?

If the suitor is pious, color isn`t a drawback. However, try talking to your father kindly, so that he approves of your marriage with contentment, and that is better for you.