Fajr

When Sayyiduna Adam alay his salam descended on the Earth from Heaven, it was the time of night, and it was the first time he had seen this world. He was in a state of shock as he had never seen darkness or night before [as in Jannah, night does not exist][1]. When dawn broke, he prayed 2 cycles [Rak'ah] thankfulness to Allah. One cycle thanking Allah for removing him from the darkness of the night and second Rakat for blessing him with the light of the day. He prayed these Rakahs as Nafl and it has been made Fard upon us so that the darkness of sins in which we are living in, is removed from our lives and we acquire the light of obedience.

Zohr

After midday, Sayyiduna Ibrahim alayhis salam was the first to pray Salah. He prayed 4 Rakah Salah to Allah thanking him for sending a replacement sacrifice instead of his son, Sayyiduna Ismayil alayhis salam.

• The first Rakah was prayed for removing the anxiety of his Son
• The second Rakah for the sending of the sheep as a sacrifice
• The third was prayed expressing gratefulness at the happiness of his Lord
• The fourth was prayed out of happiness due to the fact that Sayyiduna Ismayil alay his salam was ready to sacrifice his life at the command of Allah.

He prayed it as Nafl but it has been made fard upon us so that Allah gives us the power to kill our desires just as he gave Sayyiduna Ibrahim alayhis Salam the power to sacrifice his son in the path of Allah; also so that he removes from us our anxieties and he takes the Christians and Jews as our replacements and save us from the hellfire and also that he may be pleased with us and our actions.

Asr

The first to pray 'Asr was Sayyiduna Yunus alayhis salam for Allah saved him from 4 darknesses.

1. The darkness of mistakes
2. The darkness of melancholy
3. The darkness of the sea
4. The darkness of the whale's stomach 

It was Nafl for him but made fard upon us so that Allah saves us from the darkness of sins, the darkness of the grave, the darkness of (the tribulations) of Qiyamat, and the darkness of hell.

Maghrib

The first to pray Maghrib was Sayyiduna Iysa alayhis salam.

• He prayed the first negating his own divinity
• The second negating his mothers divinity
• The third affirming the divinity of Allah.

It was Nafl for him but made Fard upon us so that on the day of resurrection: our accounting (for sins and rewards) is made easy for us; we are saved from the fire of hell and granted salvation from the great agitation that will take place on that day; and finally, that we remove ourselves from our self conceited pride and we specially humble ourselves for the sake of Allah.

Isha

The first to pray Isha Salah was Sayyiduna Musa alayhis salam, when he was returning from the Madayin[2] and He forgot his way. He was overcome by 4 problems:

1. Sadness due to separation from his wife
2. Worry for his children
3. Anxiety on behalf of his Brother
4. Concern of being captured by Firawn.

When Allah granted him salvation from all his worries, he prayed 4 Rakah Nafl Salah which has been made Fard upon us so that Allah also shows us the path [to salvation]; that He blesses us in our works; that He grants us union with our beloveds, and grant us victory over our enemies.

Reference: Fatawa Ridawiyyah Vol 5, Pages 68-69, Barakatur Raza Porbandar Edition

Translated and compiled by Sayyid Ali Amjadi

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Footnotes

[1] "..there is no day and night in Jannah, the inhabitants of Jannah will always stay in 'Nur'" Tafseer Khazain ul Irfaan, Surah 19 Verse 61

[2] Madayin is a city in the Arabian Peninsula which Sayyiduna Musa alayhis salam passed through

http://thesunniway.com/articles/item/194-secrets-pertaining-to-the-times-of-salah