Two weeks before her fateful maiden voyage, Lightoller boarded the RMS Titanic in Belfast and acted as first officer for the sea trials. Captain Edward J. Smith gave Henry Wilde, of the Olympic, the post of chief officer, demoting the original appointee William McMaster Murdoch to first officer and Lightoller to second officer. The original second officer, David Blair, was excluded from the voyage altogether, while the ship's roster of junior officers remained unchanged. Blair's departure from the crew caused a problem as he had the key to the ship's binocular case. Because the crew lacked access to binoculars, Lightoller promised to purchase them when the Titanic got to New York.
On the night of 14 April 1912, Lightoller commanded the last bridge watch prior to the ship's collision with an iceberg before being relieved by Murdoch. Lightoller had retired to his cabin and was preparing for bed when he felt the collision. Wearing only his pyjamas, Lightoller hurried out on deck to see what had happened, but seeing nothing retired back to his cabin. Deciding it would be better to remain where other officers knew where to find him if they needed him, he lay awake in his bunk until fourth officer Joseph Boxhall summoned him to the bridge. He pulled on trousers and a navy-blue sweater over his pyjamas and also donned (along with socks and shoes) his officer's overcoat and cap. Once the fate of the ship became clear, second officer Lightoller immediately went to work assisting in the evacuation of the passengers into the lifeboats.
Lightoller was notably stricter than some of the other officers in observing the rule of "women and children first", interpreting it almost to the point of "women and children only". Lightoller took charge of lowering the lifeboats on the port side of the Titanic. As the water came up onto the boat deck, Lightoller attempted to launch Collapsible B, a smaller Englehardt lifeboat with canvas sides that was stowed atop the officers' quarters, on the port side. The collapsible boat fell onto the deck upside down. Lightoller then crossed over to the starboard side of the roof, to see if he could help with Collapsible A and saw Murdoch working on the falls when a huge wave washed him overboard into the sea. That was the last time Lightoller saw the First Officer. As the ship sank, seawater washed over the entire bow, producing a large wave that rolled aft along the boat deck. Seeing crowds of people run away from the rising water and Collapsible A washing away, Lightoller decided he could do no more, and dived into the water from the roof of the officers' quarters.
Surfacing, he spotted the ship's crow's nest, now level with the water, and started to swim towards it as a place of safety before remembering that it was safer to stay away from the foundering vessel. Then Lightoller was sucked under, as water flooded down one of the forward ventilators. He was pinned there against the grating for some time by the pressure of the incoming water. A blast of hot air from the depths of the ship erupted out of the ventilator and blew him to the surface. He was pulled down again against another grating. He did not know how he got away but he did. He came to the surface again and realized he couldn’t swim properly because of the weight of the Webley revolver he was carrying in his coat pocket, which he then swiftly discarded. Following this, he saw Collapsible B floating upside down with several swimmers hanging on to it. He swam to it and held himself to it by a rope at the front. Then the Titanic's Number 1 (forward) funnel broke free and hit the water, washing the collapsible further away from the sinking ship.
Second officer Lightoller climbed on the boat and took charge, calming and organising the survivors (numbering around thirty) on the overturned lifeboat. He led them in yelling in unison "Boat ahoy!" but with no success. During the night a swell arose and Lightoller taught the men to shift their weight with the swells to prevent the craft from being swamped. If not for this, they would have been thrown into the freezing water again. At his direction, the men kept this up for hours until they were finally rescued by another lifeboat. Second officer Lightoller was the last survivor taken on board the rescue ship RMS Carpathia.
After the sinking, Lightoller published a testimony in the Christian Science Journal crediting his complete faith in God for his survival.
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