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Both Rhombic and Monoclinic sulphur consist of $S_8$ molecules packed together. Yet the former is more stable below $114^{\circ}C$ at 1 atm and spontaneously converts to monoclinic sulphur above that temperature. Does this have something to do with the crystal structure? Gibbs equation tells us that structures with higher entropy are preferred at a higher temperature.

Even at the same temperature we can see that rhombic form is more common at higher pressures. Is pressure decreasing the entropy and favouring one form over another?

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Does that mean a monoclinic structure has higher entropy and lower enthalpy, if that's true why is entropy higher? Or is my hypothesis wrong and it's based on something completely different.

Tatai
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  • "Does this have something to do with the crystal structure?" Yes. ;-) – Karl Aug 29 '21 at 12:00
  • @Karl, and could you give me a hint please : )(or even the answer if you want to) – Tatai Aug 29 '21 at 12:22
  • Well, have you had a look a the two crystal stuctures of sulphur? (I haven't, that's your homework. ;) ) – Karl Aug 29 '21 at 12:33
  • @Karl I suppose the monoclinic structure will have lesser symmetry, but if this answer is to be believed it's not that straightforward. https://physics.stackexchange.com/questions/43492/does-high-entropy-means-low-symmetry Now I'm in high school and the only book for physical chem I know about is Atkins, maybe you can suggest some other one : ) – Tatai Aug 29 '21 at 13:00
  • @Karl, even if my first hypothesis about the entropy being higher is somewhat correct, I feel that I don't exactly know the reason, and I'm clutching at straws lol – Tatai Aug 29 '21 at 13:03
  • Have a look at these questions: https://chemistry.stackexchange.com/questions/141580/which-allotropes-of-sulfur-exist-naturally ... https://chemistry.stackexchange.com/questions/80823/does-sulfur-have-various-allotropes-at-room-temperature ... https://chemistry.stackexchange.com/questions/72807/are-allotropes-of-sulfur-two-different-phases ... https://chemistry.stackexchange.com/questions/8438/reaction-between-zinc-and-sulfur ... https://chemistry.stackexchange.com/questions/27833/why-does-sulfur-form-s8-instead-of-s3/27877 – Nilay Ghosh Aug 30 '21 at 04:22
  • Alternatively, you can look at the phase diagram of sulfur. – Nilay Ghosh Aug 30 '21 at 04:30

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