What should one who doubts the validity of his ablution and performs it frequently do?
Whoever doubts the validity of his ablution after finishing it, his ablution is valid. This is because the default is the validity of the ablution, and because doubt after finishing an act of worship doesn`t affect its validity. And Allah the Almighty knows best.
What is the expiation for breaking fast due to being on a journey, or being sick, or being in a state of menstruation?
No expiation is due on the aforesaid categories, but they are obliged to make up for the missed fast. However, if any of them failed to do so while being able to, and the next Ramadhaan has come, then making up for those days is incumbent on him/her , and paying the ransom as well. And Allah Knows Best.
Is it permissible for someone to make a supplication to Allah to marry an already married, or an engaged woman?
No, it isn`t, and the person who does so is sinful before Allah, The Almighty.
What is the ruling on wiping the head during ablution from behind a barrier like a headscarf (hijab)?
The obligation in ablution is to wipe some of the head; it is not a condition to wipe all of it. As for one who has a turban or headscarf on their head, it is permissible for them to wipe over it after wiping a part of their head in any place. This is easily done at the front of the head. This means the woman begins by wiping the front of her head from under the headscarf, then completes the wiping to the back of the head from over the headscarf. If the woman wipes over the headscarf on her head and the moisture reaches the scalp or some hair within the boundaries of the head, it suffices for wiping the head. And Allah the Almighty knows best.