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The hosts finished day two on 54/1 for an overall lead of 249 runs on a deteriorating track.
Rohit's 162-run partnership with Ajinkya Rahane dragged the hosts back into the contest, before England dismissed both in the final session.
Bowling all-rounder Chris Woakes and rookie pacer Olly Stone will be vying for the final spot in the playing eleven.
Captain Virat Kohli waged a lone battle with 72, while the duo of James Anderson and Jack Leach destroyed India.
India, who lost the wicket of Rohit Sharma early, need a further 381 runs while visitors England need nine wickets.
The England captain became the first player to score a double century in his 100th Test.
Off-spinner Dom Bess ripped the heart out of their middle order to reduce them to 257/6 at the close on day three of the opening Test.
The 30-year-old registered his second double century in three matches as England amassed 555/8 on a flat wicket at the MA Chidambaram Stadium.
Root partnered Sibley in a marathon 200-run stand to help England post a solid 263/3 at stumps.
The tourists overturned a 37-run deficit after the first innings to win a sixth successive Test in Sri Lanka.