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High temperature X-ray powder diffraction measurements of rubidiumpolyphosphate, Rb 2 { ∞  1 } [P 2 O 6 ] were carried out with a position sensitive detector (PSD) and analysed by the Rietveld method. Three new high temperature phases were identified. The monoclinic [ P 2 1 / n , a  = 12.1249(3) Å,  b  = 4.2279(1) Å,  c  = 6.4761(2) Å,  β  = 96.006(2)° room-temperature modification RbPO 3 -T, transforms at  T c   = 661 K to orthorhombic RbPO 3 -H ( Pbnm ) with the lattice constants  a  = 13.1674(4) Å,  b  = 4.5657(1) å and  c  = 6.1183(2) å (750 K). A continuous transition at  T c   = 914 K leads to RbPO 3 -HT ( Bbmm , 940 K) with  a  = 13.3517(4) Å,  b  = 4.5917(1) Å and  c  = 6.1665(2) Å, for which the empirical power law behaviour of the order parameter  Q  is  Q  ∼ ( T − T c  )  β   with  β  near 0.2 for  T c   &gt;  T  &gt; 0.8 T c  . There are saturation effects below 0.8 T C  .

Structural phase transitions of rubidiumpolyphosphate, Rb 2 { ∞ 1 } [P 2 O 6 ]