Riot police use a water cannon to disperse opposition demonstrators as they block the city's main highway during a protest against Nicolas Maduro's government in Caracas on Feb. 14, 2014.

Venezuelan authorities have freed 25 student protesters pending trial and said that 74 others arrested after this week's deadly political turmoil would be processed within hours.

Demonstrators were still gathering in various cities as they have done since Wednesday. In a more affluent part of eastern Caracas, police on Friday used tear gas and water cannons to clear a square of about 1,000 protesters, some of whom lit fires and threw stones at the security forces.

The protesters also briefly blocked a major highway nearby, denouncing President Nicolas Maduro over a litany of grievances – including the handling of demonstrations, after three people were shot dead this week following an opposition-led march.

Speaking at a televised event in the city center alongside top officials from the ruling Socialist Party and pro-government sports stars and entertainers, Maduro said he would not let the protesters cause chaos by closing important arteries.

"I'm not going to allow it. Enough! We will unblock them legally, and we won't let them block any more," he said. "The people have a right to their lives. How can four little crazy guys come along and try to close highways?"

The protesters who gathered in Caracas' Altamira Square, a heartland of past opposition activism, have said they will defy the president's ban on demonstrations until he resigns.

They blame Maduro for problems ranging from high inflation and shortages of basic products to widespread corruption and one of the worst murder rates in the world.

Maduro, a 51-year-old former union activist and bus driver, has accused his foes of seeking a coup against him similar to one that briefly toppled his predecessor Hugo Chavez in 2002.

However, there is no indication that the demonstrations threaten to oust him, nor that the military – whose role was crucial to Chavez's 36-hour unseating – will turn against the president.

The protests could give Maduro a chance to unite competing factions in the Socialist Party, split the opposition where many moderates oppose the street tactics, and distract the public's attention from economic problems. He has called on supporters to march "for peace" in the capital on Saturday.

Venezuela's state prosecutor said late on Friday that 25 people were freed pending trial out of 99 people arrested nationwide in connection with the violence of the last two days. The other 74 would be processed in the coming hours, the prosecutor said.

Reuters