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1.
Thermal and calorimetric studies were carried out on M(IO3)2·6H2O and M(IO3)2·6D2O forM 2+=Ca2+ and Sr2+, using DTA and DSC methods. The thermal behaviour of the ordinary and deuterated hydrates is outlined and the differences observed between them are discussed. The enthalpies of the phase transitions were determined. The H f o for Ca(IO3)2·6H2O, Ca(IO3)2·6H2O(D2O) and Sr(IO3)2·6H2O(D2O) were calculated from the H deh data and comments are made on the isotope effect observed.
Zusammenfassung Mittels DTA- und DSC-Methoden wurden Me(IO3)2·6H2O und Me(IO3)2·6D2O (mitMe 2+=Ca2+ und Sr2+) thermisch und kalorimetrisch untersucht. Es wird ein Überblick über das thermische Verhalten ordentlicher und deuterierter Hydrate gegeben, in dem auch die Unterschiede zwischen beiden diskutiert werden. Die Enthalpien der untersuchten Phasenumwandlungen wurden bestimmt. Aus den Daten für Hdeh wurde Hf von Ca(IO3)2·6H2O, Ca(IO3)2H2O(D2O) und Sr(IO3)2·6H2O(D2O) berechnet und Bemerkungen zum beobachteten Isotopeneffektes gemacht.
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2.
The thermal dehydration and decomposition of M(IO3)2·2H2O (M 2+=Ni2+ and Zn2+) and their deuterates were investigated by DTA and DSC methods. The data obtained confirm their onestage dehydration and their decomposition to the respective oxides. Ni(IO3)2·2H2O and Ni(IO3)2·2D2O, were more stable than Zn(IO3)2·2H2O and Zn(IO3)2·2D2O. A considerable isotope effect was observed in relation toT deh for Ni(IO3)2·2H2O and Ni(IO3)2·2D2O, which was explained by the presence of structural changes well differentiated from the dehydration process for the deuterate. The data obtained for both pairs of dihydrates were used to determine ΔH f o for Ni(IO3)2·2H2O and Ni(IO3)2·2D2O.  相似文献   

3.
The complexation reactions between Ag+, Hg2+ and Pb2+ metal cations with aza-18-crown-6 (A18C6) were studied in dimethylsulfoxide (DMSO)–water (H2O) binary mixtures at different temperatures using the conductometric method. The conductance data show that the stoichiometry of the complexes in most cases is 1:1(ML), but in some cases 1:2 (ML2) complexes are formed in solutions. A non-linear behaviour was observed for the variation of log K f of the complexes vs. the composition of the binary mixed solvents. Selectivity of A18C6 for Ag+, Hg2+ and Pb2+ cations is sensitive to the solvent composition and in some cases and in certain compositions of the mixed solvent systems, the selectivity order is changed. The values of thermodynamic parameters (ΔH co, ΔS co) for formation of A18C6–Ag+, A18C6–Hg2+ and A18C6–Pb2+ complexes in DMSO–H2O binary systems were obtained from temperature dependence of stability constants and the results show that the thermodynamics of complexation reactions is affected by the nature and composition of the mixed solvents.  相似文献   

4.
The solid-state coordination reaction: Nd(NO3)3·6H2O(s)+4Ala(s) → Nd(Ala)4(NO3)3·H2O(s)+5H2O(l) and Er(NO3)3·6H2O(s)+4Ala(s) → Er(Ala)4(NO3)3·H2O(s)+5H2O(l) have been studied by classical solution calorimetry. The molar dissolution enthalpies of the reactants and the products in 2 mol L–1 HCl solvent of these two solid-solid coordination reactions have been measured using a calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpies of [Nd(Ala)4(NO3)3·H2O, s, 298.2 K] and[Er(Ala)4(NO3)3·H2O, s,298.2 K] at 298.2 K have been determined to be Δf H m 0 [Nd(Ala)4(NO3)3·H2O,s, 298.2 K]=–3867.2 kJ mol–1, and Δf H m 0 [Er(Ala)4(NO3)3·H2O, s, 298.2 K]=–3821.5 kJ mol–1. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

5.
The complex formation between Cu2+, Zn2+, Tl+ and Cd2+ metal cations with macrocyclic ligand, dibenzo- 18-crown-6 (DB18C6) was studied in dimethylsulfoxide (DMSO)–ethylacetate (EtOAc) binary systems at different temperatures using conductometric method. In all cases, DB18C6 forms 1:1 complexes with these metal cations. The stability constants of the complexes were obtained from fitting of molar conductivity curves using a computer program, Genplot. The non-linear behaviour which was observed for variations of log K f of the complexes versus the composition of the mixed solvent was discussed in terms of changing the chemical and physical properties of the constituent solvents when they mix with one another and, therefore, changing the solvation capacities of the metal cations, crown ether molecules and even the resulting complexes with changing the mixed solvent composition. The results show that the selectivity order of DB18C6 for the metal cations in pure ethylacetate and pure dimethylsulfoxide is: Tl+ > Cu2+ > Zn2+ > Cd2+ but the selectivity order is changed with the composition of the mixed solvents. The values of enthalpy changes (ΔH°C) for complexation reactions were obtained from the slope of the van’t Hoff plots and the changes in standard enthalpy (ΔS°C) were calculated from the relationship: ΔG°C,298.15H°C − 298.15 ΔS°C. The obtained results show that in most cases, the complexes are enthalpy stabilized, but entropy destabilized and the values of ΔH°C and ΔS°C depend strongly on the nature of the medium.  相似文献   

6.
The complexation reactions between Mg2+, Ca2+, Ag+ and Cd2+ metal cations with N-phenylaza-15-crown-5 (Ph-N15C5) were studied in acetonitrile (AN)–methanol (MeOH), methanol (MeOH)–water (H2O) and propanol (PrOH)–water (H2O) binary mixtures at different temperatures using the conductometric method. The conductance data show that the stochiometry of all of the complexes with Mg2+, Ca2+, Ag+ and Cd2+ cations is 1:1 (L:M). The stability of the complexes is sensitive to the solvent composition and a non-linear behaviour was observed for variation of log K f of the complexes versus the composition of the binary mixed solvents. The selectivity order of Ph-N15C5 for the metal cations in neat MeOH is Ag+>Cd2+>Ca2+>Mg2+, but in the case of neat AN is Ca2+>Cd2+>Mg2+>Ag+. The values of thermodynamic parameters (ΔH c o , ΔS c o ) for formation of Ph-N15C5–Mg2+, Ph-N15C5–Ca2+, Ph-N15C5–Ag+ and Ph-N15C5–Cd2+ complexes were obtained from temperature dependence of stability constants and the results show that the thermodynamics of complexation reactions is affected by the nature and composition of the mixed solvents.  相似文献   

7.
A solid complex Eu(C5H8NS2)3(C12H8N2) has been obtained from reaction of hydrous europium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen⋅H2O) in absolute ethanol. IR spectrum of the complex indicated that Eu3+ in the complex coordinated with sulfur atoms from the APDC and nitrogen atoms from the o-phen. TG-DTG investigation provided the evidence that the title complex was decomposed into EuS. The enthalpy change of the reaction of formation of the complex in ethanol, Δr H m θ(l), as –22.214±0.081 kJ mol–1, and the molar heat capacity of the complex, c m, as 61.676±0.651 J mol–1 K–1, at 298.15 K were determined by an RD-496 III type microcalorimeter. The enthalpy change of the reaction of formation of the complex in solid, Δr H m θ(s), was calculated as 54.527±0.314 kJ mol–1 through a thermochemistry cycle. Based on the thermodynamics and kinetics on the reaction of formation of the complex in ethanol at different temperatures, fundamental parameters, including the activation enthalpy (ΔH θ), the activation entropy (ΔS θ), the activation free energy (ΔG θ), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained. The constant-volume combustion energy of the complex, Δc U, was determined as –16937.88±9.79 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16953.37±9.79 and –1708.23±10.69 kJ mol–1, respectively.  相似文献   

8.
Thirteen solid ternary complexes Ln(Pdc)3(Phen) (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;) have been synthesized in absolute ethanol by rare-earth element chloride low hydrate reacting with the mixed ligands of ammonium pyrrolidinedithiocarbamate (APdc) and 1,10-phenanthroline · H2O (o-Phen · H2O) in the ordinary laboratory atmosphere without any cautions against moisture or air sensitivity. IR spectra of the complexes showed that the Ln3+ ion was coordinated with six sulfur atoms of three Pdc and two nitrogen atoms of o-Phen · H2O. It was assumed that the coordination number of Ln3+ is eight. The constant-volume combustion energies of the complexes, Δc U, were determined by a precise rotate-bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, Δc H m o , and standard molar enthalpies of formation, Δf H m o were calculated. The text was submitted by the authors in English.  相似文献   

9.
The processes of thermal dehydration and decomposition of Mn(NO3)2 ·.6H2O and its deuterated analogue were studied by DTA, TG and DSC. Comparisons were made between the data obtained for the two compounds. The following phase transitions were observed: melting of the compound; dehydration to monohydrate; dehydration of the monohydrate, accompanied by its partial decomposition to MnO2; and decomposition of the anhydrous nitrate to MnO2.The DSC data were used to determine the enthalpies of the phase transitions, and those corresponding to the partial dehydration were compared with the calculated ones. The formal kinetic parameters (E * andA) for the three stages (without the melting stage) were calculated from the TG curves, and the corresponding kinetic equations are reported.
Zusammenfassung Mittels DTA, TG und DSC wurde der Verlauf der thermischen Dehydratation und Zersetzung von deuteriertem und undeuteriertem Mn(NO3)2·6H2O untersucht und die erhaltenen Ergebnisse beider Verbindungen miteinander verglichen. Folgende Phasenumwandlungen konnten beobachtet werden: Schmelzen der Verbindung; Dehydratation bis zum Monohydrat; Dehydratation des Monohydrates unter teilweiser Zersetzung zu MnO2; Zersetzung von wasserfreiem Nitrat zu MnO2. DSC-Daten wurden zur Bestimmung der Enthalpien für die Phasenumwandlungen benutzt, die so ermittelten Ergebnisse für die partielle Dehydratation wurden mit den berechneten verglichen. Anhand der TG-Kurven wurden die formellen kinetischen Parameter (E * undA) der drei Schritte (ohne Schmelzvorgang) berechnet und die entsprechenden kinetischen Gleichungen beschrieben.
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10.
Low-temperature heat capacities of a solid complex Zn(Val)SO4·H2O(s) were measured by a precision automated adiabatic calorimeter over the temperature range between 78 and 373 K. The initial dehydration temperature of the coordination compound was determined to be, T D=327.05 K, by analysis of the heat-capacity curve. The experimental values of molar heat capacities were fitted to a polynomial equation of heat capacities (C p,m) with the reduced temperatures (x), [x=f (T)], by least square method. The polynomial fitted values of the molar heat capacities and fundamental thermodynamic functions of the complex relative to the standard reference temperature 298.15 K were given with the interval of 5 K. Enthalpies of dissolution of the [ZnSO4·7H2O(s)+Val(s)] (Δsol H m,l 0) and the Zn(Val)SO4·H2O(s) (Δsol H m,2 0) in 100.00 mL of 2 mol dm–3 HCl(aq) at T=298.15 K were determined to be, Δsol H m,l 0=(94.588±0.025) kJ mol–1 and Δsol H m,2 0=–(46.118±0.055) kJ mol–1, by means of a homemade isoperibol solution–reaction calorimeter. The standard molar enthalpy of formation of the compound was determined as: Δf H m 0 (Zn(Val)SO4·H2O(s), 298.15 K)=–(1850.97±1.92) kJ mol–1, from the enthalpies of dissolution and other auxiliary thermodynamic data through a Hess thermochemical cycle. Furthermore, the reliability of the Hess thermochemical cycle was verified by comparing UV/Vis spectra and the refractive indexes of solution A (from dissolution of the [ZnSO4·7H2O(s)+Val(s)] mixture in 2 mol dm–3 hydrochloric acid) and solution A’ (from dissolution of the complex Zn(Val)SO4·H2O(s) in 2 mol dm–3 hydrochloric acid).  相似文献   

11.
The efflorescence and deliquescence processes of Mg(NO3)2 aerosol particles deposited on ZnSe substrate have been investigated through in situ Fourier transform infrared-attenuated total reflection (FTIR-ATR) technique at the molecular level. At relative humidity (RH) of ∼3%, Mg(NO3)2 particles existed as amorphous states. The amorphous Mg(NO3)2 particles were transformed into crystalline Mg(NO3)2 · nH2O (n ≤ 5) with slight increasing of RH. Thermodynamically stable Mg(NO3)2·6H2O crystals were gradually formed on the particle surface and started to be dissolved at the saturation point (∼53% RH). At the same time, a continuous phase transition from Mg(NO3)2 · nH2O (n≤5) to Mg(NO3)2·6H2O occurred on the particle surface. This led the solid particles to completely deliquesce at 76% RH, which was much higher than the saturation point of 53% RH. In the efflorescence process, Mg(NO3)2 droplets entered into the supersaturated region due to the gradual evaporation of water. Finally, amorphous particles were formed when RH decreased below 5%. In the FTIR-ATR spectra of the supersaturated Mg(NO3)2 droplets, the absorbance of the symmetric stretching vibration of NO 3 (v 1- NO 3 ) clearly became stronger. It resulted from the continuous formation of solvent share ion pairs (SIPs), and even the contact ion pairs (CIPs) between Mg2+ and NO 3 . Supported by the Trans-Century Program Foundation for the Talents by the Ministry of Education of China, the National Natural Science Foundation of China (Grant Nos. 20073004, 20473012, and 20673010), the 111 Project (B07012), and the State Key Laboratory of Physical Chemistry for Solid Surface of Xiamen University  相似文献   

12.
朱翔  黄薇  何成  段春迎 《无机化学学报》2010,26(12):2138-2142
由缩氨基脲和2-喹啉醛合成了席夫碱配体H2L,并与过渡金属离子Cd2+组装得到了四边形配合物CQ。用X射线衍射对配合物的晶体结构进行了测定,发现其具有I41/a空间群。通过荧光测试发现该配合物在CH3CN溶液中具有较强的荧光,加入间苯二甲酸、对苯二甲酸阴离子后荧光发生淬灭,而加入邻苯二甲酸阴离子荧光无变化,可以将邻苯二甲酸阴离子从其他2种二酸阴离子中区分出来。  相似文献   

13.
Conductance measurements are reported for nickel(II), cupper(II), silver(I) and cadmium(II), salts in acetonitrile (AN)–dimethylformamide (DMF) binary solvents containing macrocyclic ligand, 1,10-dibenzyl-1,10-diaza-18-crown-6 (DBDA18C6) at different temperatures. The changes in molar conductance caused by addition of DBDA18C6 to solutions were analyzed by non-linear least squares to give stability constants of 1:1 metal cation–DBDA18C6 complexes. The results show that the stabilities of the complexes are sensitive to solvent composition and in some cases the sequence of stabilities is changed with changing the composition of the mixed solvents. The values of thermodynamic quantities (ΔH°c and ΔS°c) for formation of DBDA18C6-Ni2+, DBDA18C6-Cu2+, DBDA18C6-Ag+ and DBDA18C6-Cd2+ complexes were obtained from temperature dependence of the stability constants and the results show that the values of ΔH°c and ΔS°c for these complexes are sensitive to the nature and composition of AN–DMF binary solutions, but they do not vary monotonically with the solvent composition.  相似文献   

14.
The Er3+–Yb3+ codoped Al2O3 has been prepared by the sol–gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3 · 5H2O] and ytterbium nitrate [Yb(NO3)3 · 5H2O]. The phase structure, including only two crystalline types of doped Al2O3 phases, θ and γ, was obtained for the 1 mol% Er3+ and 5 mol% Yb3+ codoped Al2O3 at the sintering temperature of 1,273 K. By a 978 nm semiconductor laser diodes excitation, the visible up-conversion emissions centered at about 523, 545, and 660 nm were obtained. The temperature dependence of the green up-conversion emissions was studied over a wide temperature range of 300–825 K, and the reasonable agreement between the calculated temperature by the fluorescence intensity ratio (FIR) theory and the measured temperature proved that Er3+–Yb3+ codoped Al2O3 plays an important role in the application of high temperature sensor.  相似文献   

15.
The solid-state coordination reactions of lanthanum chloride with alanine and glycine, and lanthanum nitrate with alanine have been studied by classical solution calorimetry. The molar dissolution enthalpies of the reactants and the products in 2 mol L-1 HCl solvent of these three solid-solid coordination reactions have been measured using an isoperibol calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpies have been determined to be Δf H m θ[La(Ala)3Cl3·3H2O(s), 298.2 K]= -3716.3 kJ mol-1, Δf H m θ [La(Gly)3Cl3·5H2O(s), 298.2 K]= -4223.0 kJ mol-1 and Δf H m θ [La(Ala)4(NO3)3·H2O(s), 298.2 K]= -3867.57 kJ mol-1, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

16.
A novel solid complex, formulated as Ho(PDC)3 (o-phen), has been obtained from the reaction of hydrate holmium chloride, ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol, which was characterized by elemental analysis, TG-DTG and IR spectrum. The enthalpy change of the reaction of complex formation from a solution of the reagents, ΔrHmθ (sol), and the molar heat capacity of the complex, cm, were determined as being –19.161±0.051 kJ mol–1 and 79.264±1.218 J mol–1 K–1 at 298.15 K by using an RD-496 III heat conduction microcalorimeter. The enthalpy change of complex formation from the reaction of the reagents in the solid phase, ΔrHmθ(s), was calculated as being (23.981±0.339) kJ mol–1 on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. The thermodynamics of reaction of formation of the complex was investigated by the reaction in solution at the temperature range of 292.15–301.15 K. The constant-volume combustion energy of the complex, ΔcU, was determined as being –16788.46±7.74 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHmθ, and standard enthalpy of formation, ΔfHmθ, were calculated to be –16803.95±7.74 and –1115.42±8.94 kJ mol–1, respectively.  相似文献   

17.
The sol-gel process was applied to the preparation of Sm2+ ion-doped silicate glasses, which show persistent spectral hole burning at room temperature. The gels synthesized by the hydrolysis of metal alkoxides and SmCl3·6H2O were heated in air at 500°C, were then reacted with H2 gas to form the Sm2+ ion. The Al2O3−SiO22 glasses are appropriate to reduce the Sm3+ ion with H2 gas and show intense photoluminescence of Sm2+ ion. Persistent spectra hole burning was observed in the excitation spectrum for the7F05D0 transition of the Sm2+ ion by the irradiation of DCM dye laser. The hole width and depth were ∼16 cm−1 and ∼10% of the total intensity, respectively, at 20°C.  相似文献   

18.
通过溶剂热法合成了2种三维微孔锌金属有机框架材料,其分子式为[Zn3(DBA)(OH)(1,10-phen)2]n (1)和{[Zn2(HDBA)(4,4′-bipy)1.5]·H2O}n (2)(H5DBA=3,5-二(2′,4′-对羧基苯基)苯甲酸;1,10-phen=1,10-菲咯啉;4,4′-bipy=4,4′-联吡啶)。结构分析表明,配合物1为三核锌基金属单元的三维微孔骨架,配合物2为双核锌基的微孔结构。与2相比,配合物1在水中具有较强的发光性能,可作为检测Fe3+、Cr2O72-和丙酮分子的发光传感器,具有较高的选择性和灵敏度。  相似文献   

19.
采用一步溶剂热法,以Cu(NO_3)_2·3H_2O为铜源,乙二醇(EG)为还原剂,聚乙烯吡咯烷酮(PVP)为表面活性剂,高温条件下制备形貌可控的Cu_2O空心球纳米材料。研究Cu(NO_3)_2·3H_2O与PVP的质量比值(w_(Cu(NO_3)_2·3H_2O)/w_(PVP))对Cu2O结构、形貌、比表面积以及光吸收特性的影响,并结合光催化机理讨论其对Cu_2O光催化性能的影响。此外,通过改变反应时间来研究Cu_2O的生长过程。结果表明,w_(Cu(NO_3)_2·3H_2O)/w_(PVP)=45时,得到的形貌为空心球表面覆盖纳米刺的Cu_2O纳米材料光催化性能最佳,在可见光辐照10 min的条件下,对甲基橙的降解率达94.3%。  相似文献   

20.
A new unsymmetrical solid Schiff base (LLi) was synthesized using L-lysine, o-vanillin and 2-hydroxy-l-naphthaldehyde. Solid lanthanum(III) complex of this ligand [LaL(NO3)]NO3·2H2O have been prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as: dα/dt=Ae−E/RT(1−α)2. The kinetic parameters (E, A), activation entropy ΔS # and activation free-energy ΔG # were also gained.  相似文献   

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