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So I'm just wondering why the Saha and Boltzmann distributions behave differently as temperature increases?

I know one is for ionization levels while the other is for energy levels but is that the answer?

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It's likely due to a combination of two reasons, one of which you already mentioned:

  1. As you state, the Saha equation relates the ionization levels while the Maxwell-Boltzmann distribution deals with the energy levels
  2. The Saha equation incorporates quantum mechanical effects in deriving it's equation while the Maxwell-Boltzmann consider quantum effects negligible.

I recommend checking out Fundamentals of Plasma Physics by J Bittencourt, as the Maxwell-Boltzmann distribution and Saha ionization equations are well covered in the book.

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The Saha equation takes into account free electrons considering the Heisenberg uncertainty princple and Pauli exclusion princple. See: http://www.phy.ohiou.edu/~mboett/astro401_fall12/saha.pdf

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