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(ADC Reference Voltage)/(2^n) where n is the number of bits the ADC has.
So at 5V, the minimum a 10-bit ADC can detect is 5/4096 = 4.88 mV.
So no. Also, remember the thermocouple can output NEGATIVE voltages at certain temperatures so if it's measuring cold your PIC won't work either (and may be damaged). You need a very large gain, very quiet, differential amplifier that may need to be bipolar (depending on the temperature you are going to encounter).
I agree that a PIC cannot measure a thermocouple with any realistic accuracy.
However, a thermocouple won't damage a PIC when the signal goes negative. The absolute maximum signals for a 16F877A is -0.3 V or -20 mA. You won't get either of those figures out of a thermocouple.
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