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.
Is washing both openings (Istinjaa`) a must before every ablution?
Washing the front and back openings (Istinjaa`) is a must in case they have an impurity, but if they do not, there is no need for that, and Istinjaa` is not a condition for the validity of ablution.
Is it permissible for a woman to conclude her marriage without the approval of her family?
No marriage is permissible without the presence of a guardian and two trust worthy witnesses, and the woman whose family had denied her right in getting married to a God-fearing, financially and physically capable man should go to the court.
Is committing Zina (Adultery and extramarital sex) without the intention of getting pregnant or deflowered considered full Zina?
All perfect praise be to Allah the Lord of the Worlds. May Allah`s peace and blessings be upon our Prophet Mohammad and upon all his family and companions.
The Messenger of Allah (PBUH) says: "The eyes commit fornication, the hands, the feet, and the private parts." [Musnad Ahmad, P.3912]. Sheikh Shu`aib `Arn`oot graded this Hadith as sound. What you are asking about is far graver. Generally speaking, sincere repentance erases sins, good deeds erase bad deeds, and fearing Allah stops one from committing this heinous act. In addition, the devil is man`s worst enemy and whoever surrenders themselves to the wolf will be eaten. And Allah The Almighty Knows Best.