Two crystal structures of bromine sorption complexes of vacuum dehydrated Cd(ll)-exchanged zeolite A have been determined by single-crystal xray diffraction techniques in the cubic space group Pm3m at 21(1) ℃. Both crystals were ion exchanged in flo...
Two crystal structures of bromine sorption complexes of vacuum dehydrated Cd(ll)-exchanged zeolite A have been determined by single-crystal xray diffraction techniques in the cubic space group Pm3m at 21(1) ℃. Both crystals were ion exchanged in flowing streams of exchange solution In which mole ratio of Cd(NO3)2 and Cd(OOCCH3)B was 1:1 with a total concentration of 0.05 M. First crystal was dehydrated at 450℃ and 2 ×10-6 Torr for two days. Second crystal was dehydrated at 650℃ and 2 ×10-6 Torr for two days. Both crystals were then treated with 160 Torr for two days. Second crystal was dehydrated at 650℃ and 2 × 10-6 Torr for two days. Both crystals were then treated with 160 Torr of zeolitically dried bromine vapor at 24℃. Full-matrix least-squares refinements of toe first crystal(a: 12.250(1) A )· and the second crystal(a: 12.204(2) A ) have contecoed to final error indices, Rl:0.075 and Ra:0.079 with 212 reflections, and Rl : 0.089 and Ra = 0.078 with 128 reflections, respectively, for which I >3σ(I). Crystallographic analyses of both crystals show that six Cd2+ ions are located on two different threefold axes of unit cell associated with 6-ring oxygens. Each 4.5 Cd2+ ion is recessed ca.0. 441 A Into the large cavity to complex either with Brsor with Br3from the (111) plane of 0(3), whereas each 1.5 Cd2+ ions recessed ca. 0.678 A into we sodalite unit. Approximately 1.5 Br5-and 1.5 Br3-ions are sorbed per unit cell. Each Brsion interacts and stabilized by complexing with two Cd2+ ions and framework oxide ions, while each Br3ion interacts with one Cd2+ ion and framework oxide ions. Because of residual water molecules the following reactions may be occurred inside of zeolite cavity: