Friday, May 24, 2019

thermodynamics - Degrees of freedom and temperature


I quote the following lines directly from the Wikipedia page titled "Heat capacity":



"...rotational kinetic energy of gas molecules stores heat energy in a way that increases heat capacity, since this energy does not contribute to temperature."



Why doesn't rotational energy contribute to temperature?



Answer




For example, rotational kinetic energy of gas molecules stores heat energy in a way that increases heat capacity, since this energy does not contribute to temperature.




This description is misguiding in two ways.


First, the statement that


rotational energy does not contribute to temperature


makes an impression that temperature is a quantity that is closely connected with the translational kinetic energy, but not rotational kinetic energy. But that is false; according to classical theory (applicable when temperatures are high) in thermodynamic equilibrium, all quadratic degrees of freedom, translational and rotational, correspond to kinetic energy $k_BT/2$ on average.


It is only true that rotational energy does not contribute to translational kinetic energy of molecules, since the two energies are exclusive contributions to total kinetic energy.


Second, heat capacity when molecules are allowed to rotate is not higher because rotational energy does not contribute to translational kinetic energy of molecules.


It is higher because for the same temperature, such system has higher energy than system without rotation. This is because there are additional degrees of freedom, to which corresponds additional average kinetic energy.


Equilibrium implies temperature implies average energies of molecules. Value of average kinetic energies of molecules neither implies temperature exists nor implies temperature is only connected to translational kinetic energy.


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