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1.
Two solid-state coordination compounds of rare earth metals with glycin, [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O melted at 342.90 K, while [ErY(Gly)6(H2O)4](ClO4)6·5H2O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol−1 and 53.9 J K−1 mol−1 for [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O, 1.82 kJ mol−1 and 5.5 J K−1 mol−1 for [ErY(Gly)6(H2O)4](ClO4)6·5H2O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.  相似文献   

2.
We have measured Raman and infrared spectra of α-Ge(HPO4)2·H2O compound at room temperature. The analysis of vibrational modes indicated the presence of two non-equivalent HPO42− units in agreement with 31P nuclear magnetic resonance measurements. A tentative assignment of all the observed modes is proposed based on the previous works reported for other hydrogenphosphate-based compounds.  相似文献   

3.
The thermal decomposition mechanisms and the intermediate morphology of MgCl2·6H2O and MgCl2·H2O were studied using integrated thermal analysis, X-ray diffraction, scanning electron microscope and chemical analysis. The results showed that there were six steps in the thermal decomposition of MgCl2·6H2O: producing MgCl2·4H2O at 69 °C, MgCl2·2H2O at 129 °C, MgCl2·nH2O (1 ≤ n ≤ 2) and MgOHCl at 167 °C, the conversion of MgCl2·nH2O (1 ≤ n ≤ 2) to Mg(OH)Cl·0.3H2O by simultaneous dehydration and hydrolysis at 203 °C, the dehydration of Mg(OH)Cl·0.3H2O to MgOHCl at 235 °C, and finally the direct conversion of MgOHCl to the cylindrical particles of MgO at 415 °C. To restrain the sample hydrolysis and to obtain MgCl2·H2O, MgCl2·6H2O was first calcined in HCl atmosphere until 203 °C when MgCl2·H2O was obtained; HCl gas was then turned off and the calcination process continued, producing Mg3Cl2(OH)4·2H2O calcined at 203 °C, Mg3(OH)4Cl2 at 220 °C and MgO at 360 °C. The temperature of producing MgO from calcination of MgCl2·H2O was lower (360 °C) than that from MgCl2·6H2O (415 °C) because of its more reactive intermediate products: the irregular shape and tiny needle-like Mg3Cl2(OH)4·2H2O particles and the uneven surface porous Mg3(OH)4Cl2 particles. The MgO particles obtained at 360 °C had a flake structure.  相似文献   

4.
Rare-earth perchlorate complex coordinated with glycine [Nd2(Gly)6(H2O)4](ClO4)6·5H2O was synthesized and its structure was characterized by using thermogravimetric analysis (TG), differential thermal analysis (DTA), chemical analysis and elementary analysis. Its purity was 99.90%. Heat capacity measurement was carried out with a high-precision fully-automatic adiabatic calorimeter over the temperature range from 78 to 369 K. A solid-solid phase transformation peak was observed at 256.97 K, with the enthalpy and entropy of the phase transformation process are 4.438 kJ mol−1 and 17.270 J K−1 mol−1, respectively. There is a big dehydrated peak appears at 330 K, its decomposition temperature, decomposition enthalpy and entropy are 320.606 K, 41.364 kJ mol−1 and 129.018 J K−1 mol−1, respectively. The polynomial equations of heat capacity of this compound in different temperature ranges have been fitted. The standard enthalpy of formation was determined to be −8023.002 kJ mol−1 with isoperibol reaction calorimeter at 298.15 K.  相似文献   

5.
H2O + Ni(NO3)2 binary system were investigated in the temperature range from −25 °C to 55 °C. The solid-liquid equilibria of the ternary system H2O + Fe(NO3)3 + Ni(NO3)2 were studied using a synthetic method based on conductivity measurements. Tow isotherms were established at 0 °C and 30 °C, and the appearing stable solid phases are iron nitrate nonahydrate (Fe(NO3)3·9H2O), iron nitrate hexahydrate (Fe(NO3)3·6H2O), nickel nitrate hexahydrate (Ni(NO3)2·6H2O) and nickel nitrate tetrahydrate (Ni(NO3)2·4H2O).  相似文献   

6.
A complex of holmium perchlorate coordinated with l-glutamic acid, [Ho2(l-Glu)2(H2O)8](ClO4)4·H2O, was prepared with a purity of 98.96%. The compound was characterized by chemical, elemental and thermal analysis. Heat capacities of the compound were determined by automated adiabatic calorimetry from 78 to 370 K. The dehydration temperature is 350 K. The dehydration enthalpy and entropy are 16.34 kJ mol−1 and 16.67 J K−1 mol−1, respectively. The standard enthalpy of formation is −6474.6 kJ mol−1 from reaction calorimetry at 298.15 K.  相似文献   

7.
合成了两种稀土高氯酸盐与L 脯氨酸配合物的晶体.经热重、差热、化学分析及对比有关文献,知其组成是[Pr2(L Pro)6(H2O)4](ClO4)6和[Er2(L Pro)6(H2O)4](ClO4)6,质量分数为99.24%和98.20%.选用RE(NO3)3•6H2O(RE=Pr,Er)、L Pro、NaClO4•H2O和NaNO3作辅助物,使用具有恒温环境的反应热量计,以2 mol•L-1 HCl作溶剂,分别测定了[2RE(NO3)3•6H2O+6L Pro+6NaClO4•H2O]和{[RE2(L PrO)6(H2O)4](ClO4)6+6NaNO3}在298.15 K时的溶解热.设计一热化学循环求得化学反应的反应焓ΔrHm分别是:63.904 kJ•mol-1和91.017 kJ•mol-1,经计算得配合物[RE2(L Pro)6(H2O)4](ClO4)6(s)在298.15 K时的标准生成焓ΔfHm(298.15 K)分别是-6 594.78 kJ•mol-1和-6 532.87 kJ•mol-1.  相似文献   

8.
镧石型碳酸镨钕[(PrNd)2(CO3)3·8H2O,LPN]在95℃的不同起始pH值的溶液中陈化不同时间所得样品的XRD衍射图证明了LPN向碱式碳酸镨钕[(PrNd)(OH)(CO3),BPN]的相态转变。为此,详细研究了这一相态转变的反应条件以及粒子特征变化。结果表明:LPN是由片状或条状结晶连生而成的聚集体,具有大的粒度和小的堆密度。当在热的水溶液中陈化时,由于水解反应而发生由LPN向BPN的相转变。这一相转变可以在95℃下pH=7以上的溶液中发生,其转化率随起始溶液pH值的升高和陈化时间的延长而增大。随着相转变的进行,溶液的pH值开始下降明显,而后趋于平缓。相应地,大的团聚体颗粒解散成小的单个粒子,导致粒度减小,分布变窄,氯根含量降低和堆密度的增大。而且,这些变化直接与溶液pH值和陈化时间相关。据此,发展了一种新的制备具有高堆密度、低氯根含量、细粒度和窄分布的新方法,而且通过改变相转变条件可以方便地调谐颗粒特征。  相似文献   

9.
利用精密绝热热量仪测定了化合物配合物Zn(Met)3(NO3)2·H2O (s) (Met=L-α-蛋氨酸)在78-371 K温区的摩尔热容. 通过热容曲线解析, 得到了该配合物的起始脱水温度为TD=325.10 K. 将该温区的摩尔热容实验值用最小二乘法拟合得到了摩尔热容(Cp)对约化温度(T)的多项式方程, 由此计算得到了配合物的舒平热容值和热力学函数值. 基于设计的热化学循环, 选择100 mL of 2 mol·L-1 HCl为量热溶剂, 利用等温环境溶解-反应热量计, 得到了298.15 K配合物的标准摩尔生成焓为ΔfHm0[Zn(Met)3(NO3)2·H2O(s),s]=-(1472.65±0.76) J·mol-1.  相似文献   

10.
本文研究了镧石型碳酸镨钕[(PrNd)2(CO33·8H2O,LPN]在95℃的不同起始pH值的溶液中陈化不同时间所得样品的XRD衍射图,证明所得样品为碱式碳酸镨钕[(PrNd)(OH)(CO3),BPN]。为此,详细研究了这一相态转变的反应条件以及粒子特征变化。结果表明:LPN是由片状或条状结晶连生而成的聚集体,具有大的粒度和小的堆密度。当在热的水溶液中陈化时,由于水解反应而发生由LPN向BPN的相转变。这一相转变可以在95℃下pH=7以上的溶液中发生,其转化率随起始溶液pH值的升高和陈化时间的延长而增大。随着相转变的进行,溶液的pH值开始下降明显,而后趋于平缓。相应地,大的团聚体颗粒解散成小的单个粒子,导致粒度减小,分布变窄,氯根含量降低和堆密度的增大。而且,这些变化直接与溶液pH值和陈化时间相关。据此,发展了一种新的制备具有高堆密度、低氯根含量、细粒度和窄分布的新方法,而且通过改变相转变条件可以方便地调谐颗粒特征。  相似文献   

11.
To study the Ru-M interactions and their effects on 31P NMR, complexes [Ru(CO)3(Ph2Ppy)2] (py = pyridine) (1) and [Ru(CO)3(Ph2Ppy)2MCl2] (M = Zn, 2; Cd, 3; Hg, 4) were calculated by density functional theory (DFT) PBE0 method. Moreover, the PBE0-GIAO method was employed to calculate the 31P chemical shifts in complexes. The calculated 31P chemical shifts in 1-3 follow 2 > 3 > 1 which are consistent to experimental results, proving that PBE0-GIAO method adopted in this study is reasonable. This method is employed to predict the 31P chemical shift in designed complex 4. Compared with 1, the 31P chemical shifts in 2-4 vary resulting from adjacent Ru-M interactions. The Ru → M or Ru ← M charge-transfer interactions in 2-4 are revealed by second-order perturbation theory. The strength order of Ru → M interactions is the same as that of the P-Ru → M delocalization with Zn > Cd > Hg, which coincides with the order of 31P NMR chemical shifts. The interaction of Ru → M, corresponding to the delocalization from 4d orbital of Ru to s valence orbital of M2+, results in the delocalization of P-Ru → M, which decreases the electron density of P nucleus and causes the downfield 31P chemical shifts. Except 2, the back-donation effect of Ru ← M, arising from the delocalization from s valence orbital of M2+ to the valence orbital of Ru, is against the P-Ru → M delocalization and results in the upfield 31P chemical shifts in 4. Meanwhile, the binding energies indicate that complex 4 is stable and can be synthesized experimentally. However, as complex [Ru(CO)3(Ph2Ppy)2HgCl]+5 is more stable than 4, the reaction of 1 with HgCl2 only gave 5 experimentally.  相似文献   

12.
合成了稀土(钬, Ho)-氨基酸(甘氨酸, C2H5O2N)二元配合物Ho(NO3)3(C2H5O2N)4·H2O, 并且通过化学分析、元素分析和红外(IR)光谱对配合物进行了表征. 用高精度全自动绝热量热仪, 测定了该配合物在80-390 K温度区间的定压摩尔热容(Cp,m). 利用实验测定的热容数据, 采用最小二乘法, 将热容曲线上热容峰以外的两段平滑区的摩尔热容对折合温度进行拟合, 建立了热容随折合温度变化的多项式方程. 根据热容与焓、熵的热力学关系,计算出了配合物在80-390 K温度区间内,每隔5 K,相对于298.15 K的摩尔热力学函数(HT,m-H298.15,m)和(ST,m-S298.15,m). 通过热容曲线分析, 计算出了350 K附近转变过程的焓变(ΔtrsHm)和熵变(ΔtrsSm). 用差示扫描量热法(DSC)测定了配合物的热稳定性.  相似文献   

13.
A pure calcium borate Ca2[B2O4(OH)2]·0.5H2O has been synthesized under hydrothermal condition and characterized by XRD, FT-IR and TG as well as by chemical analysis. The molar enthalpy of solution of Ca2[B2O4(OH)2]·0.5H2O in HC1·54.582H2O was determined. From a combination of this result with measured enthalpies of solution of H3BO3 in HC1·54.561H2O and of CaO in (HCl + H3BO3) solution, together with the standard molar enthalpies of formation of CaO(s), H3BO3(s) and H2O(l), the standard molar enthalpy of formation of −(3172.5 ± 2.5) kJ mol−1 of Ca2[B2O4(OH)2]·0.5H2O was obtained.  相似文献   

14.
Dirubidium calcium tetraborate octahydrate, Rb2Ca[B4O5(OH)4]2·8H2O, was prepared by reaction of Rb-borate aqueous solution with CaCl2 and it's structure has been determined by single-crystal X-ray diffraction data. It crystallizes in the orthorhombic system, space group P212121 with unit cell parameters, Z=4, The structure contains alternate layers of [B4O5(OH)4]2− polyanions separated by water molecules and Rb, Ca cations. The isolated [B4O5(OH)4]2− is constructed from two BO3(OH) tetrahedron groups and two BO2(OH) triangular groups joined at common oxygen atoms. The two BO3(OH) tetrahedron groups are further linked by means of an oxygen bridge across the ring. The Ca2+ ion displays seven coordination, while the two non-equivalent Rb+ ions display nine and seven coordination, respectively. Infrared and Raman (4000-400 cm−1) spectra of Rb2Ca[B4O5(OH)4]2·8H2O were recorded at room temperature and analyzed. Fundamental vibrational modes were identified and band assignments were made. The dehydration of this hydrated mixed borate occurs in one step and leads to an amorphous phase which undergoes a crystallization.  相似文献   

15.
The two new compounds, Sr4Cu3(AsO4)2(AsO3OH)4·3H2O (1) and Ba2Cu4(AsO4)2(AsO3OH)3(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As2O5-H2O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å3, Z=4 for 1; space group P42/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å3, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu2+-(XO4)3− layers (X=P5+, As5+) linked by M cations (M=alkali, alkaline earth, Pb2+, or Ag+) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu2O8 centrosymmetric dimers crosslinked by As1φ4 tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu2O8 centrosymmetric dimers of CuO5 edge-sharing polyhedra, crosslinked by As1O4 tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.  相似文献   

16.
The objectives of this study were to address uncertainties in the solubility product of (UO2)3(PO4)2⋅4H2O(c) and in the phosphate complexes of U(VI), and more importantly to develop needed thermodynamic data for the Pu(VI)-phosphate system in order to ascertain the extent to which U(VI) and Pu(VI) behave in an analogous fashion. Thus studies were conducted on (UO2)3(PO4)2⋅4H2O(c) and (PuO2)3(PO4)2⋅4H2O(am) solubilities for long-equilibration periods (up to 870 days) in a wide range of pH values (2.5 to 10.5) at fixed phosphate concentrations of 0.001 and 0.01 M, and in a range of phosphate concentrations (0.0001–1.0 M) at fixed pH values of about 3.5. A combination of techniques (XRD, DTA/TG, XAS, and thermodynamic analyses) was used to characterize the reaction products. The U(VI)-phosphate data for the most part agree closely with thermodynamic data presented in Guillaumont et al.,(1) although we cannot verify the existence of several U(VI) hydrolyses and phosphate species and we find the reported value for formation constant of UO2PO4 is in error by more than two orders of magnitude. A comprehensive thermodynamic model for (PuO2)3(PO4)2⋅4H2O(am) solubility in the H+-Na+-OH-Cl-H2PO4-HPO2−4-PO3−4-H2O system, previously unavailable, is presented and the data shows that the U(VI)-phosphate system is an excellent analog for the Pu(VI)-phosphate system.  相似文献   

17.
A novel Mo(V) diphosphate Sr(MoO)2P2O7 has been synthesized. It crystallizes in the space group P21/n with a=7.925(1) Å, b=7.739(1) Å, c=9.485(1) Å and β=91.05(1)°. Its original framework consists of MoP2O11 units built up of one P2O7 group sharing two apices with one MoO6 octahedron. The MoP2O11 units share corners, forming [MoP2O10] chains running along [101]. The assemblage of these chains forms the [Mo2P4O16] intersecting tunnel framework. The Sr2+ cations are located at the tunnel intersection, showing a distorted cubic coordination. This structure is compared to those of Ba(MoO)2P2O7 and LiMoOP2O7, which are also built up of MoP2O11 units forming [MoP2O10] chains, but with different configurations.  相似文献   

18.
The enthalpies of solution of NaRb[B4O5(OH)4]·4H2O in approximately 1 mol dm−3 aqueous hydrochloric acid and of RbCl in aqueous (hydrochloric acid + boric acid + sodium chloride) were determined. From these results and the enthalpy of solution of H3BO3 in approximately 1 mol dm−3 HCl(aq) and of sodium chloride in aqueous (hydrochloric acid + boric acid), the standard molar enthalpy of formation of −(5128.02 ± 1.94) kJ mol−1 for NaRb[B4O5(OH)4]·4H2O was obtained from the standard molar enthalpies of formation of NaCl(s), RbCl(s), H3BO3(s) and H2O(l). The standard molar entropy of formation of NaRb[B4O5(OH)4]·4H2O was calculated from the Gibbs free energy of formation of NaRb[B4O5(OH)4]·4H2O computed from a group contribution method.  相似文献   

19.
Two oxoborates, (Pb3O)2(BO3)2MO4 (M=Cr, Mo), have been prepared by solid-state reactions below 700 °C. Single-crystal XRD analyses showed that the Cr compound crystallizes in the orthorhombic group Pnma with a=6.4160(13) Å, b=11.635(2) Å, c=18.164(4) Å, Z=4 and the Mo analog in the group Cmcm with a=18.446(4) Å, b=6.3557(13) Å, c=11.657(2) Å, Z=4. Both compounds are characterized by one-dimensional chains formed by corner-sharing OPb4 tetrahedra. BO3 and CrO4 (MoO4) groups are located around the chains to hold them together via Pb–O bonds. The IR spectra further confirmed the presence of BO3 groups in both structures and UV–vis diffuse reflectance spectra showed band gaps of about 1.8 and 2.9 eV for the Cr and Mo compounds, respectively. Band structure calculations indicated that (Pb3O)2(BO3)2MoO4 is a direct semiconductor with the calculated energy gap of about 2.4 eV.  相似文献   

20.
The compounds M[PO2(OH)2]2·2H2O (M=Mg, Mn, Fe, Co, Ni, Zn, Cd) were prepared from super-saturated aqueous solutions at room temperature. Single-crystal X-ray structure investigations of members with M=Ni, Zn, Cd were performed at 295 and 120 K. The space-group symmetry is P21/n, Z=2. The unit-cell parameters are at 295/120 K for M=Ni: a=7.240(2)/7.202(2), b=9.794(2)/9.799(2), c=5.313(1)/5.285(1) Å, β=94.81(1)/94.38(1)°, V=375.4/371.9 Å3; M=Zn: a=7.263(2)/7.221(2), b=9.893(2)/9.899(3), c=5.328(1)/5.296(2) Å, β=94.79(1)/94.31(2)°, V=381.5/377.5 Å3; M=Cd: a=7.356(2)/7.319(2), b=10.416(2)/10.423(3), c=5.407(1)/5.371(2) Å, β=93.85(1)/93.30(2)°, V=413.4/409.1 Å3. Layers of corner-shared MO6 octahedra and phosphate tetrahedra are linked by three of the four crystallographically different hydrogen bonds. The fourth hydrogen bond (located within the layer) is worth mentioning because of the short Oh?O bond distance of 2.57-2.61 Å at room temperature (2.56-2.57 Å at 120 K); only for M=Mg it is increased to 2.65 Å. Any marked temperature-dependent variation of the unit-cell dimension is observed only vertical to the layers. The analysis of the infrared (IR) spectroscopy data evidences that the internal PO4 vibrations are insensitive to the size and the electronic configuration of the M2+ ions. The slight strengthening of the intra-molecular P-O bonds in the Mg salt is caused by the more ionic character of the Mg-O bonds. All IR spectra exhibit the characteristic “ABC trio” for acidic salts: 2900-3180 cm−1 (A band), 2000-2450 cm−1 (B band) and 1550-1750 cm−1 (C band). Both the frequency and the intensity of the A band provide an evidence that the PO2(OH)2 groups in M[PO2(OH)2]2·2H2O compounds form weaker hydrogen bonds as compared with other acidic salts with comparable O?O bond distances of about 2.60 Å. The observed shift of the O-H stretching vibrations of the water molecule in the order M=Mg>Mn≈Fe≈Co>Ni>Zn≈Cd has been discussed with respect to the influence of both the character and the strength of M↔H2O interactions.  相似文献   

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