It's been 30 years since Liverpool last won the league, in which time rivals United have claimed an impressive 13 Premier League titles.
Barnes was part of the last Liverpool squad that won the old first division in the 1989-90 season, and accepted it's been United who have performed the more consistently in the years since.
However he believes it's Liverpool's time to end their title drought, which can come a step closer with a win over the Red Devils.
Speaking on behalf of bookmaker comparison site BonusCodeBets.co.uk, Barnes said: "You now what’s going to happen from Liverpool’s perspective, they’re going to perform to the maximum, or close to the maximum, they’re going to be very consistent.
"Man Utd on their day, depending on how they play, can cause problems, as you saw when they played against Man City in the league.
"But I just feel Liverpool playing at home, with the confidence they have and this determination, will have too much for United. It’ll be a tight game, but I think Liverpool will just edge it."
United are the only side to take any points off Liverpool so far in 21 games this season.
Marcus Rashford's goal back in October looked to have given United the win, until Adam Lallana's late equaliser rescued a point for Liverpool.
United may yet be without the talents of Rashford, who is struggling with an injury, but Barnes warned they still have the power to cause an upset, despite what the form books say.
"The danger for Liverpool is of course, Manchester United , Rashford and Martial, and Lingard, players they have who are quick on the counter attack can cause problems," he added.
"They will pose a threat and I think Man Utd probably do better away from home where the onus is not on them to attack all the time because they are a counter attacking team, which means they suck up pressure then catch you on the counter attack. Liverpool have to be wary."
United will no doubt be pulling out all the stops to end Liverpool's unbeaten run, as the Reds remain on course to go the whole campaign without defeat.
Yet Barnes was quick to stress the only target for Jurgen Klopp and his men is collecting that trophy in May, unbeaten or not.
Asked if he feels the Reds can go unbeaten, he replied: "You can never tell. I don’t think so. It’s a hell of a season when you’ve got teams like City, United, Arsenal , Chelsea still to play. We’ve got to go to the Etihad.
"That’s not important, what’s important is to try and win the league which is what we’re going to do, and do exactly what Jurgen Klopp has done ever since he’s been at the club - worry about the next game.
"Don’t worry about going unbeaten, worry about not losing the next game, and if that attitude means at the end of the season you've not lost, that’s the situation."