What is the ruling of Islamic Law on supplicating with other than the transmitted (Ma'thur) supplications in prayer?
All praise is due to Allah, and peace and blessings be upon our master, the Messenger of Allah.
It is permissible to supplicate (make du'a) during the prayer for anything from the affairs of religion or worldly life, and the prayer is not invalidated by doing so.
Shaykh al-Islam, the Imam an-Nawawi, may Allah have mercy on him, says: "Our madhhab [i.e., the Shafi'i madhhab] holds that it is permissible for a person to supplicate during it [the prayer] with anything that is permissible to supplicate with outside the prayer, from the affairs of religion or worldly life. He may say: 'O Allah, grant me wholesome sustenance, offspring, a house, and a beautiful young wife' — describing her; or: 'O Allah, free so-and-so from prison,' or 'destroy so-and-so,' and other such things — and none of this invalidates his prayer according to us. And this is also the view of Malik, ath-Thawri, Abu Thawr, and Ishaq." [Al-Majmu', Vol.3/P.454]. And Allah, the Exalted, knows best.
What is the ruling on istinja' after urination, and is it done with water and soap or with water only?
Istinja' from urine and stool is obligatory. It is permissible to perform istinja' with water alone, or with toilet paper alone. The best way is with toilet paper then water. If one wishes to suffice with one of them, then water is better. And Allah the Almighty knows best.
Which hour coincides with the last third of the night?
This hour could be figured out by calculating the number of night hours which start at sunset, and end at dawn break, then the total is divided on three to get the result.
Is it permissible for a woman to observe voluntary fast without her husband's permission?
A woman is not permitted to observe a voluntary fast (nafl) while her husband is present without his permission.