By use of synchrotron radiation, powder X-ray diffraction studies for cerium and praseodymium monopnictides [CeX and PrX (X=P, As, Sb and Bi)] with the NaCl-type structure have been carried out up to 40 GPa at room temperature. We have investigated in detail the pressure (P) vs. cell volume (V) relationship for CeP, CeAs and CeSb. The phase transition from the NaCl-type (B1) to the CsCl-type (B2) structure is observed at around 25 GPa for CeP and 21 GPa for CeAs. The transition pressures of both compounds are about 6 GPa higher than the results previously reported. Sevan et al. have predicted that a second isostructural B2–B2 transition for CeSb occurs at around 25.2 GPa with a volume collapse of 4%. However, we cannot find the volume collapse for CeSb at least up to 35 GPa. First-order phase transitions with the crystallographic change for PrX (X=P, As and Sb) are found at 26 GPa for PrP, 27 GPa for PrAs, 13 GPa for PrSb. The structure of the high-pressure phase of these compounds is tetragonal (distorted CsCl-type, P4/mmm). For PrBi, anomalous behavior in the X-ray diffraction pattern is observed around 4 GPa. This may be due to a pressure-induced intermediate phase. The structural phase transition in PrBi occurs at about 14 GPa. The high-pressure phases of PrBi consists of coexisting of tetragonal (distorted CsCl-type, P4/mmm) and cubic (CsCl-type, Pm3m) modifications at about 14 GPa. The bulk modulus of CeX and PrX (X=P, As, Sb and Bi) is obtained from the P–V curve fitted by the Birch equation of state. The relationship between bulk modulus and cell volume for these compounds is studied.
