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Laboratory parallel-beam transmission X-ray powder diffraction investigation of the thermal behavior of nitratine NaNO3: spontaneous strain and structure evolution

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Abstract

Present work provides in-situ structural data at a fine temperature scale from RT to the melting point of nitratine, NaNO3. From the analysis of log e 33 versus log t plots, it is possible to prove that an univocal indication on the R \( \overline{3} \) c (low temperature, LT) → R \( \overline{3} \) m (high temperature, HT) transition mechanism cannot be obtained because of the relevant role played by the arbitrary assumptions required for defining the c 0 dependence from temperature of the HT phase. This is due to the occurrence of excess thermal expansion for the HT phase. A significantly better fit for an Ising-spin structural model over a non-Ising rigid-body one has been obtained for the LT phase. Moreover, the Ising model led to a smooth variation of the oxygen site x fractional coordinate throughout the transition. The structure of the HT polymorph has been successfully refined considering an oxygen site at x, 0, ½, with 50% occupancy. Such model was the only acceptable one from the crystal chemical point of view as the alternative model (oxygen site at x, y, z with 25% occupancy) led to unrealistically aplanar \( {\text{NO}}_{3}^{ - } \) groups.

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Acknowledgments

The manuscript benefited from the constructive review of an anonymous referee and Editor A. Kavner. Financial support from Sapienza Università di Roma is acknowledged.

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  1. Dipartimento di Scienze della Terra, Sapienza Università degli Studi di Roma, P.le Aldo Moro 5, 00185, Rome, Italy

    Paolo Ballirano

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Correspondence to Paolo Ballirano.

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Ballirano, P. Laboratory parallel-beam transmission X-ray powder diffraction investigation of the thermal behavior of nitratine NaNO3: spontaneous strain and structure evolution. Phys Chem Minerals 38, 531–541 (2011). https://doi.org/10.1007/s00269-011-0425-4

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