Hi Fiorella,
In the case one does a complete photoionization model (with constant pressure or constant density) the electron temperature is not fixed, it depends on the metallicity of the nebula: colder for richer gas. Then there is a effect at low density.
The equilibrium temperature in each zone of the nebula is the result of the complex computation done by the photoionization code. This is not what PyNeb is aimed to do. PyNeb is computing the "easy" part of the final step: obtaining the emissivities from Te and Ne, that you can multiply by Xi/H+ and the volume to have the line emission.
In your case, you need to have some Te diagnostic to obtain Te, and then determine Ne from the [SIII] ratio.
Hope it helps,
Christophe