Enrique was unavailable for last Saturday's 3-0 Premier League defeat at West Brom due to a knee injury, which he picked up in training.
The left-back will continue to receive treatment as the club's Melwood training base in the hope that he will be fit to face
Captain Steven Gerrard, Luis Suarez, Glen Johnson and Martin Skrtel are also set to sit out the game as Rodgers rests a number of key players.
Morocco winger Oussama Assaidi will miss the match, as he is cup tied, having played earlier in the Europa League qualifying rounds for his previous club Heerenveen.
However Assaidi, who arrived at Anfield last week in a £2.4 million deal, will be eligible to play in the group stages if Liverpool overcome Hearts.
Andy Carroll is also in line to make his first start of the season, with a potential move to Newcastle and West Ham having stalled.
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