You have but one molecule of Hydrogen (H2), meandering about in the vast emptiness of a 1cm3 closed box, at a speed of 500 m/s, bouncing off from one wall to the next. What are the rms speed and the temperature inside the box?
500 m/s; temperature cannot be determined
Well, finding the vrmsfor this one is easy! Since we have only one molecule its speed will be its own "rms” speed -
vrms=√(v2)=√(5002)ms=500 m/s.
Now, what can we say about the temperature, T ?
Kinetic theory says, for a simple, ideal gas at a fixed volume and pressure, T and vrms are related as -
vrms=√3RTM=13MRv2rms.
But can we even use this definition here? If we have just one or a few gas molecules in a fixed volume, the assumption of kinetic theory that - at any given instant the velocity distribution of the molecules is homogenous (uniform density throughout) and isotropic (no special average direction) - will be immediately violated if we have just one molecule in the system, or if it's a small number. We cannot apply our kinetic theory of gases here to determine the temperature from the vrms.
In such cases, the definition of temperature comes from a much more generalized statistical physics point of view - as the slope of a heat gained versus entropy function, at any given value of entropy. We will have another look at this in the section for the second law of thermodynamics.