More than 150 people were hurt on Monday when local Serbs attacked UN police and Nato-led peacekeepers with rocks, hand grenades and Molotov cocktails.
Shots were also fired by both sides as the police took back two UN court building seized by the demonstrators on Friday. One Serb demonstrator was in a coma after being shot in the head.
On Tuesday, the French troops used the shock grenade and fired warning shots after a group of high-school students started throwing stones at their passing motorcade near one of the bridges that cross the Ibar river dividing the city.
No one was hurt in the incident.
The northern part of the Mitrovica is dominated by ethnic Serbs, while south of the river the population is predominantly Kosovar Albanians.
Nato-led peacekeepers were attempting to restore calm in the city on Tuesday after UN police pulled out.
Angry Serb demonstrators have been protesting against Kosovo's declaration of independence from Serbia on February 17.
Hashim Thaci, Kosovo's prime minister, has said Kosovo's minority Serbs were allowing themselves "to be manipulated by Belgrade" into engaging in violence, and vowed: "There will be no compromise with hooligans".
Serbia's minister for Kosovo appeared to encourage the protesters on Monday, urging them to be patient in their bid to return Kosovo to Serbia.
"We will protect you just like we protect the Serbs in Serbia," Slobodan Samardzic said. "We will reach the goal only if we are patient, smart and organised and if we believe in what we want to accomplish."
Vojislav Kostunica, Serbia's outgoing prime minister, condemned the UN's "use of force" and said Serbia had "begun consultations with Russia over necessary mutual reaction in order to halt all violence against the Serbs".
Russia has close ties to Serbia and has rejected Kosovo's declaration of independence.
Japan on Tuesday became the 28th country to have recognise Kosovo, joining the United States and most of the European Union including leading members Britain, France and Germany.