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Ten of the corners are in the final sector of the track; drivers change gears more than 5,000 times during the race; and, at more than 100 seconds, the lap time is the longest of the year.
Vettel noticeably backed off in the final sector of the lap and is a strong favourite for pole.
Hamilton was cleared by the stewards following an investigation into whether he had broken rules forbidding drivers from driving too slowly in the final sector of the lap and held up Mercedes driver Nico Rosberg.
The Englishman was 0.229secs and four places ahead of team-mate Fernando Alonso, who made an error in the final sector of his fastest lap and ended up 11th.
He made up the time in the final sector of the lap - almost entirely of a succession of 90-degree corners - where he was 0.4secs faster than anyone else.
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Vettel was running with lower downforce, which gives faster straight-line speed in the first and final sectors of the lap but costs speed in the middle sector, which is a series of quick corners.
With a wide variety of corners, from sweeping, high-speed corners to a tight, low-speed final sector, to one of the longest Formula One straights — a kilometer, or more than half a mile, long — the 4.5-kilometer track requires excellent aerodynamic downforce and efficiency, engine power, and both good tire grip and mechanical grip.
But although he spent the final 20 laps after their final stops tucked up right behind his team-mate, Rosberg was too canny, and they crossed the line just over a second apart, after Hamilton backed off slightly in the last sector of the final lap.
Barcelona is renowned as perhaps the toughest test for a grand prix car's all-round capabilities, its combination of long-duration corners of varying speeds and a fiddly final sector providing an examination of the machinery's aerodynamic and mechanical qualities.
"The first one is short with a medium- and two higher-speed corners, the middle sector is dominated by long straights and tight low-speed corners, while the final sector is a relentless sequence of mainly low- to medium-speed corners.
We're very strong in the final sector but have a bit of work to do in the first sector.
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