首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 187 毫秒
1.
The stability constans, 1, of each monochloride complex of Eu(III) have been determined in the methanol and water mixed system with 1.0 mol·dm–3 ionic strength using a solvent extraction technique. The values of 1 increase with an increase in the mole fraction of methanol (X S ) in the mixed solvent system when 0X S 0.40. The, distance of Eu3+–Cl in the mixed solvent system was calculated using the Born-type equation and the Gibbs' free energy derived from 1. Calculation of the Eu3+–Cl distance and the preferential solvation, of Eu3+ by water proposed the variation of the outersphere complex of EuCl2+ as follows: (1) [Eu(H2O)9]3+Cl, [Eu(H2O)8]3+Cl and [Eu(H2O)7(CH3OH)3+Cl inX S0.014, (2) [Eu(H2O)8]3–Cl and [Eu(H2O)7(CH3OH)]3+Cl in 0.014<X S <0.25 and (3) [Eu(H2O)7(CH3OH)]3–Cl and [Eu(H2O)6(CH3OH)[2 3+Cl in 0.25<X S 0.40.  相似文献   

2.
Hao  Xiang  Wei  Yongge  Zhang  Shiwei 《Transition Metal Chemistry》2001,26(4-5):384-387
The compound (Hql)2[Fe2(cit)2(H2O)2]·4H2O (1) [ql = quinoline, cit4– = C(O)(CO 2)(CH2CO 2)2], prepared by reacting ferric nitrate, sodium citrate and quinoline in a molar ratio of 1:1:1 in aqueous solution, was characterized by density measurements, elementary analysis, i.r., X-ray crystallography and magnetic measurements. The X-ray crystallography results reveal that the molecule (1) consists of a binuclear iron(III) citrate anionic complex [Fe2(cit)2(H2O)2]2– and two protonated quinolines [Hql]+. The anionic complex has a centro-symmetric structure, in which two Fe3+ ions are bridged by two 2-alkoxo groups of the two deprotonated citrate ligands. The other coordination sites of the two slightly distorted octahedra are completed by all the carboxylate groups of the two cit4– ligands in a monodentate mode, and two coordinated water molecules. Magnetic measurements indicate that the two Fe3+ ions are antiferromagnetically coupled below 200 K. A least-squares fit of variable-temperature (1.5–291 K) molar susceptibility data to a dimer model gave the coupling constant J/k = –6.35(7) K and Landé factor g = 2.052(9), where the spin-only Heisenberg–Dirac–van Vleck Hamiltonian is expressed as H = –2J S 1 S 2.  相似文献   

3.
The solubilities of lanthanum carbonate La2(CO3)3·8H2O in solutionsS 0([H+]=H mol kg–1, [Na+]=(IH) mol kg–1, [ClO 4 ]=I mol kg–1) at various fixed partial pressures of CO2 have been investigated at 25.0 °C. The hydrogen ion molality and the total molality of La(III) ion in equilibrium with the solid phase were determined by e.m.f. and analytical methods, respectively. The stoichiometric solubility constants
  相似文献   

4.
Crystallization of 2RbBr · MnBr2 · 2H2O, the only double salt obtained under standard conditions from saturated aqueous rubidium–manganese bromide solutions, was theoretically predicted using the hard and soft Lewis acids and bases concept and Pauling's rules. The RbBr—MnBr2—H2O system was thermodynamically simulated by the Pitzer model assuming a solubility diagram of three branches only: RbBr, 2RbBr · MnBr2 · 2H2O and MnBr2 · 4H2O. The theoretical result was experimentally proved at 25°C by the physicochemical analysis method and formation of the new double salt 2RbBr · MnBr2 · 2H2O was established. It was found to crystallize in a triclinic crystal system, space group –P1, a = 5.890(1) Å, b = 6.885(1) Å, c = 7.367(2) Å, = 66.01(1)°, = 87.78(2)°, = 84.93(2)°, V = 271.8(1) Å3, Z = 1, D x = 3.552 g-cm–3. The binary and ternary ion interaction parameters were calculated and the solubility isotherm was plotted. The standard molar Gibbs energy of the synthesis reaction, rG m o , of the double salt 2RbBr · MnBr2 · 2H2O from the corresponding simple salts RbBr and MnBr2 · 4H2O, as well as the standard molar Gibbs energy of formation, fG m o , and standard molar enthalpy of formation fH m o of the simple and double salts were calculated.  相似文献   

5.
Absract—Diaqua(2.2.2-Cryptand)strontium dichloride trihydrate [Sr(2.2.2-Crypt)(H2O)2]2+ · 2Cl · 3H2O (I) was prepared and studied by X-ray diffraction. The triclinic structure of I (space group P , a = 9.152 Å, b = 10.140 Å, c = 15.219 Å, = 88.84°, = 88.19°, = 87.62°, Z = 2) was solved by the direct method and refined by full-matrix least-squares calculations in the anisotropic approximation to R = 0.050 for 4188 independent reflections (CAD4 automated diffractometer, CuK radiation). The structure contains the [Sr(2.2.2-Crypt)(H2O)2]2+ host–guest cation. The Sr2+ cation resides in the 2.2.2-cryptand cavity and is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of water molecules. The Sr2+ coordination polyhedron (C.N. 10) is a highly distorted dibase-centered two-cap trigonal prism. The crystal structure of I contains a branched system of ion–ion (intermolecular) hydrogen bonds O(w)–H···Cl, which connect the complex cations, the Cl anions, and the crystal water molecules to form infinite thick layers parallel to the yz plane.  相似文献   

6.
The general thermochemical reaction LnCl3·6H2O(c)+3Hthd(1)+73.92H2O(1) = Ln(thd)3(c) +3HCl·26.64H2O(aq); rHm (Ln = Pr, Ho and thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) was employed to determine through solution-reaction calorimetry at 298.15 K the standard molar enthalpies of formation of crystalline chelates, –2434.3±11.5 (Pr) and –2384.8±11.5 (Ho) kJ mol–1. These values and the corresponding molar enthalpies of sublimation enabled the determination of the standard molar enthalpies of chelates in the gaseous phase. From these values the mean enthalpies of the lanthanide-oxygen bond, 265±10 (Pr) and 253±10 (Ho) kJ mol–1 were calculated.  相似文献   

7.
The solubility property of Zn(NO3)2–Thr–H2O system (Thr—threonine) at 25°C in the entire concentration range has been investigated by the phase equilibrium semimicromethod. The corresponding phase diagram and refractive index diagram were constructed. From the phase equilibrium results, the incongruently soluble compounds of Zn(Thr)(NO3)2 · 2H2O, Zn(Thr)2(NO3)2 · H2O, and Zn(Thr)3(NO3)2 · H2O were synthesized and characterized by IR, XRD, TG–DTG, chemical and elemental analyses. The constant-volume combustion energies of the compounds, c E, determined by precision rotating bomb calorimeter at 298.15 K, were –6266.88 ± 3.72, –9263.28 ± 2.23, and –11 423.11 ± 6.81 J/g, respectively. The standard enthalpies of combustion for these compounds, c H m ° (complex, s., 298.15 K), were calculated as –2147.40 ± 1.28, –4120.83 ± 0.99, and –6444.68 ± 3.85 kJ/mol and the standard enthalpies of formation, f H m ° (complex, s., 298.15 K), are –1632.82 ± 1.43, –1885.55 ± 1.50, and –2770.25 ± 4.21 kJ/mol. The enthalpies of dissolution of the complexes in a medium of simulated human gastric juice (37°C, pH 1, in the solution of hydrochloric acid), dis H m ° (complex, s., 310 K), which were also measured by a microcalorimeter to be 13.36 ± 0.06, 15.53 ± 0.06, and 17.04 ± 0.05 kJ/mol, respectively.  相似文献   

8.
The interactions of the sulfonium ions (CH3)3S+, (CH3)2S+CH2CO2 , and (CH3)2S+-CH2CH2CO2 with up to four water molecules have been studied by ab initio molecular orbital methods. Complexes of (CH3)3S+ with one to three water molecules involve strong electrostatic sulfur-oxygen interactions; in contrast, the sulfide (CH3)2S interacts with water molecules via weak S-H hydrogen bonds, suggesting that methyl-group transfer from (CH3)3S+ in aqueous solution involves a significant alteration of the hydration pattern around the sulfur atom. Two conformers of (CH3)2S+CH2CO2 were found that display sulfur-oxygen distances which are approximately 0.3 å less than the sum of the sulfur and oxygen van der Waals radii, indicating a strong intramolecular electrostatic interaction. For the complexes (CH3)2S+CH2CO2 ·nH2O(n =1–4), water interacts primarily with the carboxylate group via hydrogen bonds, rather than electrostatically with the sulfur atom, although in complexes with the three- and four-water complexes, the proximity of the positively charged sulfur atom to the carboxylate group significantly alters the hydration pattern compared to that in the corresponding of complexes CH3SCH2CO2 · Thus, methyl transfer from (CH3)2S+CH2CO2 to an acceptor in aqueous solution also involves substantial changes in the hydration pattern around the carboxylate group.  相似文献   

9.
The crystal structure of the paramagnetic bis(pyridine-2,6-dithiocarbomethylamide) nickel(II) nitrate (NiPDTA) is described: C18H22N6S4·(NO3)2·(H2O)1,5, monoclinic, C2/c,Z=4,a=14.705 (3) Å,b=23.254 (8) Å,c=8.383 (3) A, =98.18 (2)°,d x=1.55 gcm–3,d m=1.53 gcm–3. The structure was solved withPatterson and differenceFourier techniques and refined to a residual ofR=0.053. The nickel is surrounded by a square bipyramidal coordination of four thioamide sulfur atoms and two pyridine nitrogen atoms. Vibrational and electronic band positions for this compound are discussed.
Kristallstruktur und Spektren des Pyridin-2,6-dithiocarbomethylamid Nickel(II)-Komplexes
Zusammenfassung Die Kristallstruktur des paramagnetischen bis(Pyridin-2,6-dithiocarbomethylamid) Nickel(II)-nitrats (NiPDTA) wurde bestimmt. C18H22N6S4Ni·(NO3)2·(H2O)1,5, monoklin, C2/c,Z=4,a=14,705 (3) Å,b=23,254 (8) Å,c=8,383 (3) A, =98,18 (2)°,d x=1,55gcm–3,d m=1,53gcm–3. Das Phasenproblem wurde mittelsPatterson-und Differenz-Fourier-Synthese bestimmt und die Struktur bis zu einem kristallographischenR-Faktor vonR=0.053 verfeinert. Das Nickel-Atom ist von vier Thioamid-Schwefelatomen und zwei Pyridin-Stickstoffatomen in quadratisch-bipyramidaler Anordnung umgeben. Schwingungsspektren und Anregungsspektren des Komplexes werden diskutiert.
  相似文献   

10.
The intercalation reactions betweenn-alkylamines and -titanium phosphate in aqueous media have been investigated. The compounds with the maximum intercalation have the formula -Ti(HOPO3)2 · 2 C n H 2n+1 NH2 · H2O (n=1–10). Defined crystalline phases with lower amine content are described, the general formula being -Ti(HOPO3)2 · m C n H 2n+1 NH2 ·pH2O (m=1.0 1.3, 1.5, 1.7). Whenm=1.0 then-alkylamines form a monomolecular layer. Whenm>1.0 the layer is bimolecular. The inclination angle and the packing density of then-alkylamines in the interlayer space is determined.  相似文献   

11.
Summary The mechanism of the sorption of U on TiO2 · x H2O is investigated in absence and in presence of carbonate as function of pH. Speciation of U in solution and the state of the surface of TiO2 · x H2O are taken into account. In the experiments the mole fractions of the U species in presence of carbonate are the same as in seawater. Below pH 5 the sorption of U can be described in absence and in presence of carbonate by ion exchange of UO 2 2+ or alternatively by sorption of UO2OH+, because hydrolysis and sorption are occurring simultaneously. Above pH 5 in absence of carbonate, first pH-independent sorption of (UO2)3(OH) 7 and then (above the isoelectric point of TiO2 · x H2O) pH-dependent sorption of (UO2)3(OH) 7 are observed. In the same pH range, but in presence of carbonate, two species of U are dominating in solution, first UO2CO3OH and then UO2(CO3) 3 4– · UO2CO3OH is not sorbed in measurable amounts which causes a drastic decrease of the sorption ratio. UO2(CO3) 3 4– , which begins to dominate above pH 6 (depending on the carbonate concentration), is sorbed either by formation of TiOUO2 bonds or (at carbonate concentrations >10–2 mol/l) via carbonate bridges.
Sorption von Uranylionen an wasserhaltigem Titandioxid
  相似文献   

12.
The reaction betweenL-arabinose and hydrated uranyl salts has been investigated in aqueous solution and the solid complexes of the type UO2(L-arabinose)X 2 · 2 H2O, whereX=Cl, Br, and NO 3 , have been isolated and characterized. Due to the marked similarities with those of the structurally known Ca(L-arabinose)X 2 · 4 H2O and Mg(L-arabinose)X 2 · 4 H2O (X=Cl or Br) compounds, the UO 2 2+ ion binds obviously to twoL-arabinose moieties, through O1, O5 of the first and O3, O4 of the second molecule resulting into a six-coordinated geometry around the uranium ion with no direct U-X (X=Cl, Br or NO 3 ) interaction. The intermolecular hydrogen bonding network of the freeL-arabinose is rearranged upon uranium interaction. The -anomer configuration is predominant in the freeL-arabinose, whereas the -anomer conformation is preferred in the uranium complexes.
Darstellung, spektroskopische und Strukturanalyse von Uran-Arabinose Komplexen
Zusammenfassung Es wurde die Reaktion zwischenL-Arabinose und hydratisierten Uranylsalzen in wäßriger Lösung untersucht und kristalline Komplexe des Typs UO2(L-Arabinose)X 2 · 2 H2O mitX=Cl, Br und NO 3 isoliert und charakterisiert. Wie aus markanten Ähnlichkeiten der Komplexe mit den bekannten Verbindungen Ca(L-Arabinose)X 2 · 4 H2O und Mg(L-Arabinose)X 2 · 4 H2O (X=Cl oder Br) abzuleiten ist, bindet das UO 2 2+ -Ion mit zweiL-Arabinose Einheiten, wobei sich durch die O1,O5-Koordination des ersten und die O3,O4-Koordination des zweiten Moleküls eine sechs-koordinierte Geometrie um das Uranylion [ohne direkte U-X (X=Cl, Br oder NO 3 ) Wechselwirkung] ausbildet. Die intermolekularen Wasserstoffbrücken zeigen nach der Wechselwirkung mit dem Uranylion eine Umgruppierung. In der freienL-Arabinose ist das -Anomere vorherrschend, in den Urankomplexen hingegen das -Anomere.
  相似文献   

13.
The behaviour of thermal dehydrations of isomorphous complexes of calcium copper acetate hexahydrate, CaCu(CH3CO2)4·6H2O and calcium cadmium acetate hexahydrate, CaCd(CH3CO2)4· 6H2O was studied by means of thermal analyses and X-ray structural analysis. The enthalpy changes for the dehydration of CaCu(CH3CO2)4·6H2O and CaCd(CH3CO2)4·6H2O were 315±9.7 and 295±8.0 kJ mol–1, respectively. The DSC curves of the dehydrations indicated that the seemingly simple dehydrations are more complex than they appear at first sight. Apparent activation energies for the dehydrations of CaCu(CH3CO2)4·6H2O and CaCd(CH3CO2)4·6H2O were 85.7±7.4 and 87.9±12.5 kJ mol–1, respectively.The authors wish to express their thanks to Associate Professor Yasuhiko Yukawa of the Niigata University for the analysis of the X-ray-intensity data.  相似文献   

14.
Thermal transformations (at 340 to 390 °C) of coprecipitates of iron and cobalt acrylates, [Fe3O(CH2CHCOO)6OH][Co(CH2CHCOO)2]2.4 (1) and [Fe3O(CH2CHCOO)6OH][Co(CH2CHCOO)2]1.5·3H2O (2), are studied. The dependence of the degree of gas evolution () on time is described by the equation () wherek 1=2.3 · 1012 · exp[–49500/(RT)] s–1,k 2=6.0 · 106 · exp[–33000/(RT)] s–1 andk 1=2.6 · 1012 · exp[–49000/(RT)] s–1,k 2=6.6 · 105 · exp[–30000/(RT)] s–1 for cocrystallizates1 and2, respectively. The coefficient 1 decreases as the temperature increases. The value of 1 for compound1 is higher than that for compound2. The composition of products of the transformations of1 and2 are studied. The main solid state products of the decomposition are nanometer-sized particles of cobalt ferrite, CoFe2O4, with a narrow size distribution stabilized by the polymeric matrix. The thermal transformations of cocrystallizates1 and2 include dehydration, thermal decomposition, copolymerization in the solid state, and decarboxylation of the metallocarboxylate groups of the polymer. The effect of the ratio between the Fe clusters and the Co-containing fragments on the process of thermal transformation is analyzed.For Part 40, seeRuss. Chem. Bull., 1994,43, 2020.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 885–893, May, 1995.The authors are grateful to A. N. Titkov for optical microscopic and electron microscopic studies.  相似文献   

15.
Zhang  Cun-Gen  Tian  Guo-Hua  Ma  Zi-Feng  Yan  De-Yue 《Transition Metal Chemistry》2000,25(3):270-273
The preparation and isolation of the binuclear manganese(III) complex, [Mn(vanen)(H2O)2]2(ClO4)2 · 2H2O was accomplished by air oxidation of a solution containing H2vanen**, Et3N, and Mn(ClO4)2 · 6H2O in absolute EtOH. The crystal structure of complex was determined by X-ray crystallography, and consists of two molecules bridged by two water molecules through hydrogen bonding. The manganese atom is six-coordinate and presents a distorted octahedral coordination sphere, which consists of the two imine N atoms and two phenolic O atoms of vanen2– ligand in the equatorial plane, with Mn–N bond distances of 1.975 and 1.987 Å, and Mn–O distances of 1.867 and 1.876 Å, respectively. The non-bonding interatomic MnMn distance is 4.79 Å. In the axial direction, the elongated Mn–O(H2O) bond distances of 2.255 and 2.381 Å, respectively, are due to Jahn–Teller distortion at the d4 metal center. The presence of lattice and coordinate water molecules were also confirmed by the t.g. study and the i.r. spectra. Upon irradiation using visible light in water in the presence of p-benzoquinone, the complex demonstrates its ability to split water.  相似文献   

16.
Wang  Yao Yu  Zhou  Li Jun  Shi  Qian  Shi  Qi Zhen  Gao  Yi Ci  Hou  Xun 《Transition Metal Chemistry》2002,27(2):145-148
A MeOH solution of imidazole reacts with Cu2A4(H2O)2 [A = CH2=CHCO 2, CH2=C(Me)CO 2] to yield novel trinuclear copper(II) carboxylate complexes of general formula: Cu3A5(OH)(imH)3 [(1) A=CH2=CHCO 2; (2) A = CH2=C(Me)CO 2; imH = imidazole]. The crystal structure of (2) has been determined. The geometry of one copper(II) atom is distorted trigonal bipyramidal, and the other two copper(II) atoms are distorted square-planar. The i.r. spectra show the presence of the absorption bands of both bidentate 2-O,O and monodentate carboxylate ligands. The electronic reflectance spectra in the solid state suggest that the d–d transitions of complexes are in a trigonal bipyramidal ligand field and a square-planar ligand field. Room temperature X-band e.s.r. spectra of powdered samples with g av = 2.140 for (1) and g av = 2.092 for (2), indicate that there is no spin coupling between the copper(II) atoms.  相似文献   

17.
Complexes of S-benzyldithiocarbazate (SBDTC) with lighter and heavier metals, viz., CrIII, FeIII, SbIII, ZrIV, ThIV and UVI have been prepared and characterized by elemental analyses, conductivity measurements, and spectral studies. The complexes: [Cr(SBDTCA)3],** [Fe(SBDTCA)3], [Sb(SBDTCA)3], [Sb(SBDTCA)2Cl · H2O], [Zr(O)(SBDTCA)2 · H2O], [Th(SBDTCA)(NO3)3 · H2O)], and [U(O)2(SBDTCA)2] were all prepared in alkaline media. They were all hexa-coordinated with bidentate, uninegative chelation of the ligand. [Fe(SBDTCA)3], [Sb(SBDTCA)3] and [Sb(SBDTCA)2Cl · H2O] were strongly effective against bacteria giving clear inhibition zones with Pseudomonas aeruginosa and Bacillus cereus. The compounds showed poor antifungal activity. The antimony complexes were strongly cytotoxic against leukemic cells with CD50 values of 3.2–6.7 g cm–3 as compared to the CD50 value of 14.5 g cm–3 of the free SbCl3 molecule.  相似文献   

18.
The structure of the Cu[(2-O)(5-NO2)C6H3N–CH=CH–+PPh3]2 complex with the CuN2O2 coordination core of distorted square-planar geometry was established by X-ray diffraction analysis. The molecules in the crystal structure of the Cu[(2-O)(5-NO2)C6H3N–CH=CH–+PPh3]2 · 2CHCl3 solvate are bound via hydrogen bonds of two types, namely, C(sp 2)–H···O and C(sp 3)–H···O.  相似文献   

19.
Investigation of the aqueous lithium and magnesium halide systems   总被引:1,自引:0,他引:1  
The solubilities of the system LiBr–MgBr2–H2O have been investigated at 25°C and 50°C. It is established that the system is of a simple eutonic type. Pitzer's model is used for calculating the thermodynamic functions needed for plotting the solubility isotherms of the systems LiX–MgX2–H2O (X=Cl, Br) at 25°C. According to calculations made, the Gibbs energy of formation of LiCl·MgCl2·7H2O from simple salts is rm=–2.01 kJ-mol–1, while the value fm=–2748 kJ-mol–1 corresponds to formation from the elements.  相似文献   

20.
The aqua complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with strontium perchlorate of the composition [Sr(ClO4)L(H2O)2]+ · ClO4 · H2O (I) was synthesized and studied using X-ray diffraction analysis: space group P21/c, a = 16.195 Å, b = 11.382 Å, c = 16.646 Å, = 117.01°, Z = 4. The structure was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.069 for 4278 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains complex cation [Sr(ClO4)L(H2O)2]+ of the host–guest type. The Sr2+ cation (coordination number 9) is coordinated to all six O atoms of the L podand, O atom of a disordered ClO4 ligand, and two O atoms of two water molecules. The coordination polyhedron of Sr2+ is irregular; in a rough approximation, it can be described as a face-centered cube. The crystal structure of I contains an infinite three-dimensional network of the O–H···O hydrogen bonds joining the complex cations, ClO4 anions, and molecules of crystallization water.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号