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Summary Detailed investigations of CuCl2 hydrolysis step of Cu–Cl thermochemical cycle were carried out on various aspects: (a) characterization and thermal properties of reactants/products using X‐ray diffraction (XRD), thermogravimetry–mass spectrometry (TG‐MS), scanning electron microscopy (SEM), temperature‐programmed desorption (TPD), and extended X‐ray absorption fine structure (EXAFS); (b) performance evaluation of fixed bed hydrolysis; (c) parametric optimization with respect to S/Cu, flow rate (gas hourly space velocity, GHSV), reaction duration, temperature, and particle size; and (d) monitored hydrolysis using isothermal TG experiments at 360°C, 370°C, 380°C, 390°C, and 400°C to derive kinetic parameters rate constant (k) and activation energy (Ea) on the basis of the shrinking‐core model. 97% conversion to Cu2OCl2 at 17 630 h−1 of GHSV, 400°C was achieved using ball‐milled CuCl2 (BM6), as compared with that of 55% over commercial un–ball‐milled reactant, CuCl2 (UBM). Correspondingly, higher k value of 2.84 h−1 over BM6 as compared with 0.97 h−1 over UBM reactant at 400°C was achieved. Ea for hydrolysis of BM6 was 93 kJ/mol, while it was 106 kJ/mol for UBM as derived from the Arrhenius plot. A probable pathway for CuCl2 hydrolysis is proposed here. It was found to be diffusion controlled, and the particle size of reactant molecules affects the packing and diffusion length. Based on our investigations, it is very unlikely to get >99% phase pure product (Cu2OCl2). Cu2OCl2 is labile in nature and tends to transform into structurally similar and stable compounds CuO and CuCl2.

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Pressure induced structural phase transformation and mechanical properties of NaCl-type (B1) to CsCl-type (B2) structure in uranium monochalcogenides (UX; X = S, Se, and Te) are presented. An effective interionic interaction potential is constructed, consisting of the long-range Coulomb and the Hafemeister and Flygare type short-range overlap repulsion extended up to the second-neighbour ions and the van der Waals (vdW) interaction. Particular attention is devoted to evaluate the vdW coefficients following the Slater-Kirkwood variational method, as both the ions are polarizable. Our calculated results have revealed reasonably good agreement with the available experimental data on the phase transition pressures (P t = 81, 21, 13 GPa) and the elastic properties of UX (X = S, Se, and Te). The equation of state curves (plotted between V (P)/V (0) and pressure) for both the NaCl-type (B1) and CsCl-type (B2) structures obtained by us are in fairly good agreement with the experimental results. The calculated values of the volume collapses ( V (P)/V (0)) are also closer to their observed data. The variations of the second-and third-order elastic constants with pressure have followed systematic trends, which are almost identical to those exhibited by the measured and observed data in other compounds of the NaCl-type structure family.

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