Morning pace-setter Felipe Massa had to settle for second in his Ferrari this time, ahead of teammate Kimi Raikkonen and McLaren's Lewis Hamilton.
Sebastian Vettel was an impressive fifth for Toro Rosso, while points leader Robert Kubica (BMW) completed the top six and Hamilton's teammate Heikki Kovalainen took seventh.
After the lacklustre morning session, second practice proved much more frenetic - both in terms of close competition, and the number of incidents, as the increasingly hot conditions saw many drivers sliding through the gravel or across the asphalt run-off areas.
Both McLarens and both Ferraris took turns to lead the way during the first half of the session, with Hamilton the first of the major contenders to set a quick time after ten minutes. He stayed ahead of a quarter of an hour before being usurped by Massa, who was only on top briefly before first Kovalainen, then Raikkonen moved to the front.
But Massa responded with a 1:15.854 lap at the mid-point of the session, beating Raikkonen by 0.148 seconds. That was sufficient to keep him at the head of the order until Alonso grabbed the soft tyres and edged ahead by 0.076 seconds with seven minutes remaining.
Earlier in the session, Alonso had run off course at the 180 corner and saved a wild sideways slide on the exit of the final chicane, but the former champion was far from the only driver to make an error.
Hamilton, Jarno Trulli (Toyota) and Massa all had spectacular high-speed trips across the gravel at Estoril, with the McLaren driver's mid-session incident forcing him to change his front wing, and Massa's late mistake spoiling his soft tyre run.
The Brazilian had a similarly dramatic excursion on the exit of Imola, emerging from the gravel halfway around the Chateau d'Eau. The same area also caught out Renault's Nelson Piquet and Force India's Adrian Sutil, although all the drivers managed to avoid the barriers.
The field was extremely close throughout the session, and by the end of the 90 minutes less than one second covered the top 13 cars.
Vettel was rapid all afternoon, regularly running in the top five and using the softer Bridgestones to beat Kubica and Kovalainen to fifth.
Kubica's BMW teammate Nick Heidfeld was eighth, ahead of Piquet and Red Bull driver David Coulthard.
At the end of the session, the drivers tested the new safety car electronics system after they had taken the flag, although the device - which is designed to limit cars' speed when driving through dangerous situations - remains in the early stages of its development. Pos Driver Team Time Laps 1. Alonso Renault (B) 1:15.778 37 2. Massa Ferrari (B) 1:15.854 + 0.076 24 3. Raikkonen Ferrari (B) 1:15.999 + 0.221 42 4. Hamilton McLaren-Mercedes (B) 1:16.232 + 0.454 29 5. Vettel Toro Rosso-Ferrari (B) 1:16.298 + 0.520 42 6. Kubica BMW Sauber (B) 1:16.317 + 0.539 35 7. Kovalainen McLaren-Mercedes (B) 1:16.340 + 0.562 36 8. Heidfeld BMW Sauber (B) 1:16.458 + 0.680 43 9. Piquet Renault (B) 1:16.543 + 0.765 39 10. Coulthard Red Bull-Renault (B) 1:16.572 + 0.794 36 11. Rosberg Williams-Toyota (B) 1:16.682 + 0.904 42 12. Trulli Toyota (B) 1:16.743 + 0.965 43 13. Bourdais Toro Rosso-Ferrari (B) 1:16.758 + 0.980 42 14. Nakajima Williams-Toyota (B) 1:17.002 + 1.224 32 15. Glock Toyota (B) 1:17.092 + 1.314 39 16. Webber Red Bull-Renault (B) 1:17.106 + 1.328 38 17. Button Honda (B) 1:17.244 + 1.466 37 18. Fisichella Force India-Ferrari (B) 1:17.394 + 1.616 42 19. Barrichello Honda (B) 1:17.591 + 1.813 27 20. Sutil Force India-Ferrari (B) 1:17.868 + 2.090 33
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