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Phase transitions in K2Cr2O7 and structural redeterminations of phase II.

T J R Weakley¹, E R Ylvisaker, R J Yager

¹Department of Chemistry, University of Oregon, Eugene, OR 97403, USA.

Acta Crystallographica. Section B, Structural Science

|November 10, 2004

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Potassium dichromate (K2Cr2O7) crystals exhibit a first-order phase transition between phase II and phase I. This transition temperature is affected by included water, with a higher temperature observed on initial heating due to water pressure.

Area of Science:

Solid State Chemistry
Crystallography
Materials Science

Background:

Potassium dichromate (K2Cr2O7) exists in multiple crystalline phases.
Understanding phase transitions is crucial for materials science and chemical applications.

Purpose of the Study:

To investigate the phase transition behavior of K2Cr2O7 crystals.
To determine the phase transition temperatures and structural changes.
To elucidate the role of included water in the phase transition.

Main Methods:

Single-crystal X-ray diffraction.
Differential Scanning Calorimetry (DSC) for thermal analysis.
Analysis of mass loss during heating.

Main Results:

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A first-order phase transition from phase II (triclinic, P1) to phase I (monoclinic, P21/n) was observed.
Phase transition temperatures were determined: 544(2) K (heating, first cycle), 502(2) K (cooling), and 531(2) K (subsequent heating).
Mass loss due to included water was quantified, influencing the initial transition temperature.

Conclusions:

The phase transition is driven by structural changes related to the rotation of oxygen atoms in dichromate tetrahedra.
Included water pressure in defects elevates the transition temperature on first heating.
The study refined structural data for K2Cr2O7 and proposed relationships between different phases (II, IIb, I).