Saturday 10 November 2018

thermodynamics - Do rotational degrees of freedom contribute to temperature?


Recently I have come across a mathematical problem where I was said to calculate the temperature increase of certain mol of N2 gas confined in a room.
However, I found that there was only consideration of kinetic energy in the issue of temeperature.
My question is why don't we include rotational DOF in calculating temeperature increase?



Answer



If you start with a monatomic gas then the only degrees of freedom available are the three translational degrees of freedom. Each of them absorbs $\tfrac{1}{2}kT$ of energy, so the specific heat (at constant volume) is $\tfrac{3}{2}k$ per atom or $\tfrac{3}{2}R$ per mole.



If you move to a diatomic molecule there are two rotational modes as well - only two extra modes because rotation about the axis of the molecule has energy levels too widely spaced to be excited at normal temperatures. Each of those two rotational degrees of freedom will soak up another $\tfrac{1}{2}kT$, giving a specific heat of $\tfrac{5}{2}k$ per molecule or $\tfrac{5}{2}R$ per mole.


But the rotational energy levels are quantised with an energy spacing of $E = 2B, 6B, 12B$ and so on, where $B$ is the rotational constant for the molecule:


$$ B = \frac{\hbar^2}{2\mu d^2} $$


where $\mu$ is the reduced mass and $d$ is the bond length. So these rotational energy levels will only be populated when $kT$ is a lot greater than $B$ - say 10 to 100 times greater. You can look up the rotational constant of nitrogen, or it's easy enough to calculate, and the result is:


$$ B \approx 3.97 \times 10^{-23} \text{J} $$


which is about $3k$. So as long as the temperature is above say $30K$ the rotational modes will be excited and nitrogen will have a specific heat of $\tfrac{5}{2}R$. If you go down to temperatures of $3K$ and below then the specific heat will fall to $\tfrac{3}{2}R$ just like a monatomic gas.


The specific heat of nitrogen at constant volume is 0.743 kJ/(kg.K), and converting this to J/mole.K we get 20.8 J/(mole.K) and this is indeed 2.50R (to three significant figures).


The conformist mentions that the vibrations of the nitrogen molecule will contribute to the specific heat, and indeed they will. However the energy of the first vibrational mode is 2359 cm$^{-1}$, which converted to non-spectrogeek units is $4.7 \times 10^{-20}$ J or about $3400k$. So the vibrational mode isn't going to contribute to the specific heat until the temperature gets above 3400K.


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