Solubilities in the NaOH-TiO 2 · H 2 O-H 2 O system at 25°C were studied. The solubility isotherm was found to have two maxima. The formation of two compounds, Na 2 Ti 5 O 11 · 10H 2 O and Na 2 Ti 3 O 7 · 7H 2 O, was established.
Ксерогели гидратированных диоксидов циркония и гафния состава ZrO2 · 2.5H2O и HfO2 · 2.3H2O при нагревании дегидратируются в две стадии. Сначала из структуры соединений удаляется преимущественно молекулярная вода и образуются фазы состава ZrO2 · H2O и HfO2 · 0.5H2O. На второй стадии протекает поликонденсация ОН-групп. Оба процесса осуществляются легче для ZrO2 · 2.5H2O. При дегидратации соединения циркония также зафиксировано взаимодействие молекул воды с цирконий-кислородными мостиками. Состав соединения HfO2 · 0.5H2O следует представлять формулой Hf4O7(H2O)(OH)2.
Hydrous zirconia and hafnia xerogels of compositions ZrO2 · 2.5H2O and HfO2 · 2.3H2O are dehydrated in two steps upon heating. First, molecular water is mostly removed from the structures to form phases of compositions ZrO2 · H2O and HfO2 · 0.5H2O. Second, polycondensation of OH groups occurs. Both processes are easier for ZrO2 · 2.5H2O. Apart from these steps, the interaction of water molecules with zirconium-oxygen bridges was found to occur during dehydration of the zirconium compound. The composition of HfO2 · 0.5H2O should actually read as Hf4O7(H2O)(OH)2.
Hydrous tin dioxide xerogel with the composition SnO2 · 1.75H 2 O is built of tin-oxygen-hydroxide fragments. Water molecules (no more than 1 mol) in the grain structure are kept by hydrogen bonds. Xerogel is dehydrated in the range 50–890°C in two stages. Below 123°C, molecular water is removed and the polycondensation of ≡Sn-O(H)-Sn≡ bridge groups occurs. There also takes place the transition of some water molecules from the molecular to hydroxide form as follows: ≡Sn-O-Sn≡ + H 2 O → 2≡Sn-O-H. All processes occur within individual grains. Above 123°C, water removal is due to the polycondensation of tin-oxygen groups. As a result, grains are coarsen. After 200°C, their structure is determined as cassiterite coated by tin oxyhydrate.
Single crystals of Rb-2 [GeO2 (OH)(2)] center dot 2H(2)O are studied by X-ray diffraction. The crystals belong to the orthorhombic system, sp. gr. Pna2(1), a = 13.523( 6) angstrom, b = 8.143( 4) angstrom, c = 13.407( 6) angstrom, Z = 8, R-1 = 0.0506. In [GeO2 (OH)(2)](2-) anions, the Ge - O distances (1.71 - 1.73( 1) angstrom) are shorter than the Ge - OH distances (1.76-1.80( 1) angstrom). Anions are linked to each other by pairs of hydrogen bonds to form infinite chains. The chains are linked by hydrogen bonds involving water molecules to form a 3D structure. The assignment of the bands in the IR spectrum of the compound under study is performed.
Single crystals of Rb 2 [GeO 2 (OH) 2 ] · 2H 2 O are studied by X-ray diffraction. The crystals belong to the orthorhombic system, sp. gr. Pna 2 1 , a = 13.523(6) Å, b = 8.143(4) Å, c = 13.407(6) Å, Z = 8, R 1 = 0.0506. In [GeO 2 (OH) 2 ] 2− anions, the Ge-O distances (1.71–1.73(1) Å) are shorter than the Ge-OH distances (1.76–1.80(1) Å). Anions are linked to each other by pairs of hydrogen bonds to form infinite chains. The chains are linked by hydrogen bonds involving water molecules to form a 3D structure. The assignment of the bands in the IR spectrum of the compound under study is performed.
On the basis of structural and pH-metric titration data for suspensions of hydrated zirconium, hafnium, tin, and lead dioxides, it is demonstrated that the acidic properties become weaker while the basic properties become stronger in the sequence Hf-Zr-Sn-Pb. The dependence of these properties on the temperature of the sample pretreatment was revealed.