Black smoke from the first two votes of the conclave entering its second day has signalled the cardinals tasked with electing a new pope are still not agreed on Benedict's successor.
They are expected to hold a further two ballots later on the first full day of voting.
The cardinals reconvened for the papal conclave behind closed doors after the first round of voting on Tuesday night proved inconclusive.
Black smoke billows from the chimney of the Vatican's Sistine ChapelThey awoke to attend mass in the Pauline Chapel in the Vatican's Apostolic Palace and returned to the Renaissance splendour of the Sistine Chapel to hold two morning ballots.
All eyes remain on the chimney atop the Vatican's Sistine Chapel as the process of finding a successor to Benedict XVI, who brought a troubled eight-year papacy to an abrupt end by resigning last month, will continue until his replacement is found.
The 115 voting eligible church leaders spent the night sequestered in the Santa Marta Hotel on the edge of the Vatican's gardens, without access to television, newspapers, mobile phones or computers.
The cardinals are scheduled to hold four votes each dayThey first filed into the chapel chamber, renowned for its ceiling fresco painted by Renaissance master Michelangelo, on Tuesday morning to begin their deliberations.
Hours later after sunset, black smoke billowed from the chimney above the Vatican, indicating that no-one had gained the two-thirds majority needed to become the 266th pope.
Only the emergence of white smoke - produced by mixing the smoke from burning ballots with special flares - will signal that a new leader for the world's 1.2 billion Catholics has been chosen.
The tens of thousands that braved the rain and gathered in St Peter's Square to bear witness to the centuries-old tradition cheered in excitement or booed in mock disappointment.
Among the cardinals gathered in Rome, Italy's Angelo Scola, Brazil's Odilo Scherer and Canada's Marc Ouellet - all conservatives like Benedict - are the three favourites.
Modern-day conclaves normally last no more than a few days.
People packed St Peter's Square on Tuesday night awaiting the site of smokeHowever, there is no clear frontrunner, meaning the election could go on for much longer than the two days and four rounds of voting that it took to elect Joseph Ratzinger in 2005, following the death of John Paul II.
Some analysts have suggested that Benedict's dramatic departure - the first papal resignation in over 700 years - could push the cardinals to take an equally unusual decision and elect an outsider.
Hopes are high in the Philippines for the popular Archbishop of Manila, Luis Antonio Tagle, and on the African continent for South Africa's Wilfrid Napier, the archbishop of Durban, but in practice their chances are very slim.
Two-thirds of the cardinals are from Europe and North America and the view among many experts is that only someone with experience of the inner workings of the Vatican administration can drive reform and repair the scandal-ridden reputation of the Catholic Church.
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