Correct Option: D

Consider exactly at 4 : 00, minute hand is at position '12' and hour hand is at '4' hence angle between these two hands at 4 : 00 is 120°
Since relative speed between them is 11/2° per minute or every minute the minute hand will travel 11/2° more than the hour hand.
Then will be perpendicular to each other when the minute hand will travel (120 - 90) = 30° more than the hour hand. And time taken for this is (30)/(11/2) = 60/11 or 5 5/11 minute
Hence they will be perpendicular to each other at 4 : 11 minute : 45.45 second