South Africa set Zimbabwe 537 to win after Mulder's 147
Takudzwanashe Kaitano was the only wicket to fall with what proved the final delivery of the day on Monday as he edged seamer Corbin Bosch to Lhuan-dre Pretorius as second slip having made 12.
Fellow opener Prince Masvaure (5 no), in the side as a concussion replacement for Brian Bennett, survived a testing spell in the fading light to reach the close with Zimbabwe still needing 505 runs for victory and two days remaining.
Masvaure had two close leg before wicket appeals from South Africa's teenage fast bowler Kwena Maphaka, but with no third umpire in operation in this series, the latter was unable to challenge the decisions.
South Africa resumed their second innings on 1-49 in the morning and upped the tempo with the bat before being bowled out for 369 in 82.5 overs.
Mulder was the glue that held the innings together as he scored a second test century in his new number three position in the batting order, with his 147 coming from 206 deliveries.
He played shots all around the ground before being caught on the boundary attempting a six, topping his previous best test score of 105 not out against Bangladesh last October.
Stand-in captain Keshav Maharaj added a quick-fire 51 on a wicket that has started to turn.
Left-arm spinner Wellington Masakadza was the pick of the home bowlers with figures of 4-98, while leg-spinner Vincent Masekesa took 2-117.
A much-changed South Africa are fielding only four of the players who did duty in the World Test Championship final victory over Australia at Lord's earlier this month.
The second and final Test in this series will be played at the same venue and starts on Sunday.
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