The melting point of silicon is around 150C.
The problem is, you can't measure the centre of transistor junctions. Sensors have mass and therefore take time to heat, etc.
The engineering approach is to treat the chain [Silicon --> Package --> Heatsink -->Ambient] as a series of 'resistances' specified in degrees C per watt. Read an IC manufacturer Application Note for details. A heatsink of 2.5 degrees C per watt dissipating 20 watts would be 50 degrees above ambient - get the idea?
http://www.ferrotec.com/technology/t.../thermalRef05/
http://www.thermshield.com/.../Basic...esentation.pdf
Then the commonsense approach superimposes itself. Allow 25-35 degrees per stage. CPU Critical is set at 105degrees, heatsink about 70 degrees C. These are absolute maxima. Lower is better, as it avoids thermal cycling (= aging) of components..