The relationship is not linear because the CPU itself generates more heat, and thus has an even higher operating temperature, as it becomes hotter itself.
If the CPU was nothing but a heater then its operating temperature would rise in a "1 to 1" fashion with the rising ambients.
If your ambient rose 1°C then so too would the peak operating temperature of the "heater".
But your CPU generates more heat as it gets hotter, raising the operating temperature even more so.
As such, if your ambient rises say 4°C, your CPU's peak operating temperature may very well rise by 5 or 6°C.
The extra increase in operating temperature coming from the extra waste heat being generated from the elevated leakage within the CPU now that it is operating at the higher temperature.
A longer and more elaborate data-backed explanation can be read here:
http://forums.anandtech.com/showthread.php?t=2281195