Here is a count of how many times the Doctor (or his companion) offers someone a Jelly Baby and exactly what serial he offers it in.
The Three Doctors: 1
Robot: 1
The Ark in Space: 2
The Face of Evil: 1
The Robots of Death: 1
Image of the Fendahl: 2
The Sun Makers: 3
The Invasion of Time: 4
The Pirate Planet: 1 (Romana)
Destiny of the Daleks: 2
Nightmare of Eden: 1
The Horns of Nimon: 1
The TV Movie: 2
Total: 22