Kohli had raced to 44, his highest score in the series, and looked good but was dismissed by South Africa's most successful bowler -- off-spinner Dane Piedt -- who had figures of 4/56 to show for his efforts.
It was a flighted delivery and Kohli hit a full blooded sweep shot. But to his horror, the ball popped up after rebounding off the thigh of forward short-leg fielder Temba Bavuma and wicketkeeper Dane Vilas rushed from his position to dive forward and completed an impressive catch.
At the break, Rahane was undefeated on 31 with three boundaries.
But it will certainly be Rohit Sharma (1), whose irresponsible shot selection will be talked about for a long time to come.
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Having been dropped at slip on 0 by Hashim Amla off Kyle Abbott's bowling, Rohit decided to give Piedt the charge by lofting a flighted delivery but only to be caught by the fielder stationed at long on for that exact shot.
Wriddhiman Saha (1) was done in by a sharp inswinger from Abbott (2/21) as umpires called for tea.
He found an able ally in Rahane, who also found some form going his way, as the duo added 50 runs for the fourth wicket in only 48 minutes facing 67 balls.
Not only did they score quickly, they also showed the earlier batsmen that there were no demons in the pitch which made it even difficult to fathom some of the poor shot selections especially by Rohit, who has now wasted another golden opportunity to settle down in the Test team.
(REOPENS DEL 31)
It was Piedt again who bowled an off-break that caught Dhawan not lunging fully forward and offering his pad to be adjudged plumb in-front. Dhawan's 33 came off 85 balls with four boundaries to his credit.
The loudest cheer from the school children, who had come to watch the first day's play, was reserved for skipper Kohli.
But to Kohli's dismay, Pujara was soon sent back to the dressing room by Abbott. It was delivery that moved in after pitching as it sneaked in breaching Pujara's defence to hit the stumps. The dismissal due to the gap between bat and pad was something identical that had trouble the Saurashtra player in Australia, last year.
It was a sedate start by the Indian openers as Vijay and Dhawan scored 29 in the first 15 overs. Vijay was lucky to get a reprieve on personal score of 10 when Abbott delivery that saw him edge one to AB de Villiers at second slip was rightly ruled 'no-ball' by the third umpire CK Nandan.
However, India's most consistent batsman, who looked scratchy from the start, could not capitalise on it, uncharacteristically pushing a straighter one from Piedt to find Hashim Amla pouch one at the first slip.