Supporters of Catalan independence began occupying polling stations on Friday, setting up a possible confrontation with police who have been ordered to clear them out by Sunday morning to ensure a referendum can not go ahead.
Catalonia, one of Spain's 17 autonomous regions, has some 7.5 million people and includes the tourist-popular Mediterranean port of Barcelona, the country's second-largest city, which is home to a Catalan parliament and regional government.
The government has now launched an app that informs citizens about where to vote and the Catalan police force says its primary duty is to maintain public order, not necessarily to stop the referendum as Spanish coordination demands.
Dr James Summers is a Professor of International Law at Lancaster University.
They have been ordered to clear schools occupied by activists - including parents and their children who remained in the buildings after the end of lessons on Friday - aiming to ensure the buildings can be used for voting.
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Spain's education ministry warned in a statement that school directors in Catalonia "were not exempt from liability" if they helped to stage Sunday's referendum, which Madrid deems illegal.
"I insist: there will be no referendum on October 1st", government spokesperson Inigo Mendez de Vigo said on Friday during a press conference following the weekly cabinet meeting.
"We will vote! We will vote!" farmers chanted.
Catalan authorities have pledged to make the voting possible even if police, acting on judges' orders, manage to close polling stations and seal off ballot boxes. The EU said Catalonia would be forced out of the bloc and have to reapply to join if it leaves Spain. Yet Catalan officials have suggested that they shouldn't do so if that endangers public order.
Montserrat Aguilera wasn't intending to vote for the Catalonia region to secede from the rest of Spain. In the Spanish capital of Madrid, thousands marched to protest the separatists' attempt to break up their nation, demanding that Catalan leaders be sent to jail. It would be "sensible, reasonable and democratic to stop and say, 'there won't be a referendum, ' which [Catalan independence campaigners] know won't happen", he later told his supporters.
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"Our hope", Mitjans argued, "is that the massive presence of people prevents them from sealing off the polling stations".
Much remains unclear, including whether police will forcibly remove people who are still in the polling stations at a 6 a.m. Sunday deadline and how many of Catalonia's voters will be able to cast ballots amid the central government's crackdown.
Spain has been desperately trying to undermine the vote in recent weeks, sending thousands of national police into Catalonia, threatening people with sedition changes, and raiding sites across the area trying to find ballot papers to seize.
The region's Catalonia's foreign affairs chief has appealed for support from the European Union over Spain's measures to prevent the poll.
Maite Lopez Sanchez, 55, who came to the protest with her daughter, said Spanish institutions should "explain better what they are doing to enforce the constitution".
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In Barcelona, Francisco Morales, a 69-year-old retiree, said he was marching Saturday to defend the unity of Spain against the "lies" of Catalan separatists.