Additive reactions of Ni[(C 4H 9O) 2PS 2] 2 with ethylamine,diethylamine and triethylamine were studied by spectrophotometric methods in ethanol at several tempertures.With ethylamine,the adduct formation of NiL 2...Additive reactions of Ni[(C 4H 9O) 2PS 2] 2 with ethylamine,diethylamine and triethylamine were studied by spectrophotometric methods in ethanol at several tempertures.With ethylamine,the adduct formation of NiL 2·B and NiL 2·B 2 was established.For diethylamine and triethylamine,being of their steric hindrance effect,the formation of NiL 2·B only was concluded.Their additive equilibrium constants(lg β n)and additive molecular number(n) were discussed.Thermodynamic parameters △ r H m and △ r S m were found by the least square method.The additive equilibrium constants in the range 278 0～303 0K were described by empirical equation.展开更多
The structure of single crystal of the polyoxotungstate salt Na10{(PW9O34)2Ni4（H2O）2}·26H2O ( Na10Ni4O96P2W18H56, Mr=5371.96) has been determined by X-ray diffraction (MoK（）. Crystal data: P21/n, a=11.898（2...The structure of single crystal of the polyoxotungstate salt Na10{(PW9O34)2Ni4（H2O）2}·26H2O ( Na10Ni4O96P2W18H56, Mr=5371.96) has been determined by X-ray diffraction (MoK（）. Crystal data: P21/n, a=11.898（2）, b=16.629（4）, c=21.413（4） ?, ( = 100.59（1）o, V= 4164.5（1） ?3, Z=2, Dc = 4.284g/cm3, F（000） = 4704, ( =2.5847cm-1, final R = 0.0344, and wR= 0.0804 for 5830 independent reflections. Two B-(-PW9O349- units in the compound are linked via a set of four coplanar Ni2+ atoms, which also carry H2O ligands. The NiO6 octahedra in each centrosymmetric anion are all tetragonally elongated with their long axes parallel.展开更多
Low-temperature heat capacities of the compound Ni（C4H7O5）2·2H2O（S） have been measured with an auto- mated adiabatic calorimeter. A thermal decomposition or dehydration occurred in 350--369 K. The temperature...Low-temperature heat capacities of the compound Ni（C4H7O5）2·2H2O（S） have been measured with an auto- mated adiabatic calorimeter. A thermal decomposition or dehydration occurred in 350--369 K. The temperature, the enthalpy and entropy of the dehydration were determined to be （368.141 ±0.095） K, （18.809±0.088） kJ·mol ^-1 and （51.093±0.239） J·K^-1·mol^-1 respertively. The experimental values of the molar heat capacities in the temperature regions of 78-350 and 368-390 K were fitted to two polynomial equations of heat capacities （Cp,m） with the reduced temperatures （X）, [X=f（T）], by a least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated on the basis of the fitted polynomials. The smoothed values of the molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated with an interval of 5 K.展开更多
文摘Additive reactions of Ni[(C 4H 9O) 2PS 2] 2 with ethylamine,diethylamine and triethylamine were studied by spectrophotometric methods in ethanol at several tempertures.With ethylamine,the adduct formation of NiL 2·B and NiL 2·B 2 was established.For diethylamine and triethylamine,being of their steric hindrance effect,the formation of NiL 2·B only was concluded.Their additive equilibrium constants(lg β n)and additive molecular number(n) were discussed.Thermodynamic parameters △ r H m and △ r S m were found by the least square method.The additive equilibrium constants in the range 278 0～303 0K were described by empirical equation.
基金grants from the State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, CAS, the
文摘The structure of single crystal of the polyoxotungstate salt Na10{(PW9O34)2Ni4（H2O）2}·26H2O ( Na10Ni4O96P2W18H56, Mr=5371.96) has been determined by X-ray diffraction (MoK（）. Crystal data: P21/n, a=11.898（2）, b=16.629（4）, c=21.413（4） ?, ( = 100.59（1）o, V= 4164.5（1） ?3, Z=2, Dc = 4.284g/cm3, F（000） = 4704, ( =2.5847cm-1, final R = 0.0344, and wR= 0.0804 for 5830 independent reflections. Two B-(-PW9O349- units in the compound are linked via a set of four coplanar Ni2+ atoms, which also carry H2O ligands. The NiO6 octahedra in each centrosymmetric anion are all tetragonally elongated with their long axes parallel.
基金This work was supported by the grants from State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter+1 种基金 the Chinese Academy of Sciences (CAS) and the Science Foundation of CAS and Fujian province (2002F014,
基金Project supported by the National Natural Science Foundation of China （No. 20673050）, the Poat-doctor Start-up Foundation of Liaocheng Univer sity （No. 31805）.
文摘Low-temperature heat capacities of the compound Ni（C4H7O5）2·2H2O（S） have been measured with an auto- mated adiabatic calorimeter. A thermal decomposition or dehydration occurred in 350--369 K. The temperature, the enthalpy and entropy of the dehydration were determined to be （368.141 ±0.095） K, （18.809±0.088） kJ·mol ^-1 and （51.093±0.239） J·K^-1·mol^-1 respertively. The experimental values of the molar heat capacities in the temperature regions of 78-350 and 368-390 K were fitted to two polynomial equations of heat capacities （Cp,m） with the reduced temperatures （X）, [X=f（T）], by a least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated on the basis of the fitted polynomials. The smoothed values of the molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated with an interval of 5 K.
基金National Natural Science Foundation of China(51002126)Open Project of State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials(10zxfk30)
