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1.
锆-氘反应热力学特性研究   总被引:3,自引:1,他引:2  
The p-c-T curves and the relation between equilibrium pressure and temperature of deuterium absorption and desorption from zirconium were measured in the temperature range of 400~675 ℃. Equilibrium pressure of the absorption and desorption at different temperatures were given and then the thermodynamic parameters and the deuterium absorption capacity were determined according to Vant Hoff equation. There are different changes of enthalpy and entropy when zirconium changes to different phases. The change of enthalpy in the phase of α plus δ is -98.9 kJ·mol-1 in the temperature range of 400~475 ℃. The changes of enthalpy in the first and second plateau are -75.1 kJ·mol-1 and -161.7 kJ·mol-1, respectively in the temperature range of 525~675 ℃. The corresponding changes of entropy are -66.5 J·K-1·mol-1, -32.4 J·K-1·mol-1 and -146.5 J·K-1·mol-1, respectively. There are obvious lagging effects when zirconium desorbs deuterium.  相似文献   

2.
复盐法制备无水氯化镁的热解机理及动力学研究   总被引:4,自引:0,他引:4  
The complex compound (MgCl2·C6H5NH2·HCl·6H2O) was prepared by reaction of C6H5NH2·HCl with MgCl2·6H2O. Reaction mechanism and kinetics of the compounds decomposition were studied by means of the TG-DTA-MS coupling technique and the TG-DTA technique. The results show that there are four steps in the complex′s thermal decomposition, the first two steps correspond to the loss of six crystal waters and the last two steps loss one Aniline hydrochloride. The first three steps belong to the R2 mechanism with 2-dimentional phase boundary reaction as the control step, and the last step belongs to the D3 with 3-dimensional diffusion (sphere Jander equ.) as the control step. The apparent active energy of four steps are, 127.4 kJ·mol-1, 124.8 kJ·mol-1, 142.3 kJ·mol-1 and 329.0 kJ·mol-1, respectively and the frequency factor are 1.28 × 1018 s-1, 7.94 × 1015 s-1, 5.98 × 1016 s-1 and 4.39 × 1034 s-1, respectively.  相似文献   

3.
A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol. IR spectrum of the complex indicates that Lu3+ binds with sulfur atom in the Na(Et2dtc)3 and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, ΔrHmӨ (l), was determined to be (-32.821 ± 0.147 ) kJ·mol-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, ΔrHmӨ (s), was calculated to be (104.160 ± 0.168) kJ · mol-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (ΔHӨ), the activation entropy (ΔSӨ), the activation free energy (ΔGӨ), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, cm, was determined to be (82.23 ± 1.47) J·mol-1·K-1 by the same microcalormeter. The constant-volume combustion energy of the complex, ΔcU, was determined as (-17 898.228 ± 8.59) kJ·mol-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHmӨ, and standard enthalpy of formation, ΔfHmӨ, were calculated to be (-17 917.43 ± 8.11) kJ·mol-1 and (-859.95 ±10.12) kJ·mol-1, respectively.  相似文献   

4.
The equilibrium solubilities of the quaternary system CsCl-TmCl3-HCl-H2O was determined at 25 ℃ and the corresponding equilibrium diagram was constructed. The diagram is a complicated system with limited solid solutions and formation of a new compound 3CsCl·2TmCl3·14H2O. The new compound has been characterized by XRD, TC-DTG and fluorescence spectrometry. Results show that upconversion spectrum exhibits at 335 nm when exciting at 860 nm, and fluorescence spectrum exhibits at 295 nm and 385 nm when exciting at 240 nm. The compound loses its crystal water by four steps at 50 to 250 ℃. Using a heat conduction calorimeter, the standard molar enthalpy of dissolution of 3CsCl·2TmCl3·14H2O was determined to be (-11.601 ± 0.050) kJ·mol-1 at 298.15 K.  相似文献   

5.
纳米Mn-Zn铁氧体的制备和研究   总被引:10,自引:0,他引:10  
Nanosize manganese zinc ferrites were fabricated by hydrothermal precipitation route using Fe2(SO4)3, ZnSO4·7H2O, MnSO4·H2O as material, then some calcinated at 500 ℃ and studied by XRD, TEM, IR and VSM. The results showed that the products were spinel crystal structure and uniformly sized nanoparticles (15~25 nm) with little aggregation. The analysis of IR showed that the superficial water can be eliminated, but that was embedded in crystal lattice can not be removed by calcinating. The effect Zn content x on the lattice (a) of nanosize Mn1-xZnxFe2O4 was also discussed. The lattice of nanosize Mn1-xZnxFe2O4 decreases with x increasing; and its value deviated the standard lattice (a0) of normal size manganese zinc ferrites. A lot of water was absorbed during the hydrothermal process owing to the large surface of nanosize particles. The change of magnetic properties of MnxZn1-xFe2O4 with x increasing was studied: nanosize MnxZn1-xFe2O4 particles synthesized by us exhibited peculiar magnetic properties curve with Zn content (x) increasing, Superparamagnetic behaviors of the synthesized ZnFe2O4 samples were confirmed by magnetic characterization, which can be explained by the difference between the distribution of the metal ions (Mn2+, Zn2+ and Fe3+) among the tetrahedral (A) and the octahedral (B) sites of nanosize ferrite and that of bulk ferrite.  相似文献   

6.
The title complex was synthesized by reaction of taurine salicylic schiff base(TSSB), O-phenanthroline(phen) and cupric acetate in water-ethanol solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 498.00. The crystal structure of the title complex belongs to orthorhombic system with space group Pbcn and cell parameters: a=3.107 2(4) nm, b=1.289 09(18) nm, c= 1.034 78(14) nm; and V=4.144 7(10) nm3, Z=8, Dc=1.596 g·cm-3, μ=1.197 mm-1, F(000)=2 048. The compound is an one-dimensional chain complex of infinite length which are connected with hydrogen bonds. The Cu(Ⅱ) was coordinated by two oxygen atoms and three nitrogen while the o atoms of Ac- groups did not participate in the coordination. The Cu(Ⅱ) formed a distorted tetragonal pyramid and the capacities of coordination to Cu(Ⅱ) of atoms was discussed. Besides, the TG-IR of the complex was analyzed. The kinetics of the thermal decomposition reaction of the complex was studied under a non isothermal condition by TG-IR. TG and DTG curves indicate that the complex decomposed in three stages: (?) The kinetic parameters were obtained from the analysis of TG,DTG cures by OZAWA-Flynn-Wall method, and the activation energy and the value of A of the three stages are 74.98 kJ·mol-1, 286.65 kJ·mol-1, 87.55 kJ·mol-1; 9.66×108 s-1,1.82×1028 s-1, 3.09×103s-1, respectively.  相似文献   

7.
乐学义  童明良 《无机化学学报》2002,18(10):1023-1027
The complex [Cu(L-met)(phen)(H2O)]NO3·H2O has been synthesized and investigated by elemental analysis, molar conductivity, spectroscopic and X-ray diffraction methods, where phen=1,10-phenanthroline and L-met=L-methioninate group. The complex crystallized in the monoclinic space group P21 with a=12.053(2)?, b=6.886(1)?, c=13.385(3)?, β=113.59(3)°, V=1018.1(3)?3, Z=2,Dc=1.598g·cm-3, μ=1.223mm-1, F(000)=506, R1=0.0306, and wR2=0.0742. The copper(Ⅱ) atom is ligated in a distorted square-pyramidal geometry by two nitrogen atoms of one phen and the amino nitrogen atom , one carboxylate oxygen atom of L-met in the base plane, and an aqua at the apical position. A one-dimensional chain configuration formed by the hydrogen-bonding and weak Cu-O (the uncoordinated carboxyl oxygen atom) coordination interactions be-tween neighboring [Cu(L-met)(phen)(H2O)]+ cations. CCDC: 183368.  相似文献   

8.
杂多酸盐K7[PTi2W10O40]·6H2O与牛血清白蛋白相互作用的研究   总被引:7,自引:0,他引:7  
Under the imitated physiological condition of animal body, the interactions of heteropoly salt (PM-19) with bovine serum albumin (BSA) were investigated by fluorescence and absorption spectroscopy. It was shown that this compound had a quite strong ability to quench the fluorescence launching from BSA. After analyzing the fluorescence quenching data according to Stern-Volmer equation and Lineweaver-Burk double-reciprocal equation, we found that BSA had reacted with PM-19 and formed a certain new compound. The quenching belonged to static fluorescence quenching. According to Lineweaver-Burk equation, the forming constants of the compound (298 K: 2.68 × 105 L·mol-1; 304 K: 2.19 × 105 L·mol-1; 310 K: 1.82 × 105 L·mol-1) and the thermodynamic parameters (ΔH=-24.72 kJ·mol-1; ΔS=20.97 J·mol-1·K-1 / 20.92 J·mol-1·K-1/ 20.97 J·mol-1·K-1; ΔG=-30.97 kJ·mol-1/ -31.08 kJ·mol-1/-31.22kJ·mol-1) at the corresponding temperatures were obtained. The latter shows that binding power between them is mainly electrostatic interaction. Based on F?rster′s non-radiation energy transfer mechanism, the binding locality (r=4.14 nm) was calculated between donor and accepter. The effect of PM-19 on the conformation of BSA was also analyzed by synchronous fluorescence spectroscopy.  相似文献   

9.
Sorption behavior and mechanism of D201×4 resin for Au(III) were investigated. D201×4 resin has a good adsorptivity for Au(III) in HAc-NaAc medium at pH value of 2.63. The statically saturated Au(III) sorption capacity was 689.11 mg·g-1 resin. The Au(III) adsorbed on D201×4 resin could be eluted by 10%NH2CSNH2-1 mol·L-1 HCl(1∶1) and the elution rate was 92.2%.The adsorption of Au(III) on D201×4 follows the Freundlich isotherm. The ΔH of the adsorption was 11.03 kJ·mol-1. The sorption rate constant was 5.42×10-5 s-1. The activation energy was 13.26 kJ·mol-1. The molar coordination ratio of the functional group of D201×4 to Au(III) was about 1:1. The adsorption mechanism of resin for Au(III) was suggested according to chemical analysis and IR spectraoscopy results.  相似文献   

10.
The title compound was prepared by the solid state reaction of stoichiometric amounts of CdCl2·H2O and 4-nitroaniline . The crystal used for X-ray analysis was obtained by slow evaporation of an ethanol-aqueous solution of the solid state reaction at room temperature. The structure of compound was characterized by X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbca, a=0.77864(7)nm,b=0.72547(6)nm,c=3.3126(2)nm,Z=4,V=1.8712(3)nm3,Dc=1.890g·cm-3,μ=1.763mm-1, F(000)=1048,R=0.0300,wR=0.0697. The title compound is a typical two-dimensional organic intercalated compound. The inorganic layers of the compound are formed by CdCl6 octahedra sharing corner Cl atoms (i.e. catena-poly[dihlorocadmium-di-μ-chloro]). The organic ammonium cations are intercalated between every two metal-halogen layers and formed the organic layers of the compound through hydrogen bonding.  相似文献   

11.
Physico-chemical properties of Chitosan films   总被引:1,自引:0,他引:1  
Chitosan films obtained by dry phase inversion were prepared from an aqueous solution of chitosan in acetic acid. The films, of thickness less than 20 μm, were transparent, very flexible and had smooth surfaces. Increasing the film thickness induced an increase of the internal tensions and the consequent formation of a rough surface. Structural investigations by X-ray diffraction and Fourier transform IR analysis, showed that the chitosan films, as prepared, are amorphous. Further annealing to evaporate acetic acid and water traces, changed the amorphous phase into a more ordered phase, characterized by diffraction peaks at 2θ values of 9, 17, 20 and 23 degrees. Thermal investigations by TG, DTG, and DTA revealed that the decomposition of the chitosan films as prepared proceeds in two stages, starting from 180°C and 540°C.  相似文献   

12.
Kinetics of oxidation of xylitol and galactitol by hexacyanoferrate(III) ion in aqueous alkaline medium is reported. The reaction rate is of first order with respect to hexacyanoferrate(III) in each substrate. The reaction is first order at lower concentrations of xylitol and galactitol and tends towards zero order as the concentration increases. Similarly first order kinetics was obtained with respect to hydroxide ion at lower concentrations and tends to lower order at higher concentration in the oxidation of xylitol; in the oxidation of galactitol the reaction is first order with respect to hydroxide ion even up to manyfold variation. The course of reaction has been considered to proceed through the formation of an activated complex between [K Fe(CN)6]2– and substrate anion which decomposes slowly into radical and [K Fe(CN)6]3–. A probable reaction mechanism is proposed.
Kinetik und Mechanismus der Oxidation von Xylit und Galaktit mit Hexacyanoferrat(III) in wäßriger, alkalischer Lösung
Zusammenfassung Das Geschwindigkeitsgesetz der Titelreaktion ist in beiden Fällen erster Ordnung bezüglich Hexacyanoferrat(III). Die Oxidation ist erster Ordnung bei niedrigen Konzentrationen von Xylit und Galaktit und geht bei Erhöhung der Konzentration gegen null. In gleicher Weise wurde eine Kinetik erster Ordnung bezüglich Hydroxyl bei niedrigen Konzentrationen und eine erniedrigte Ordnung bei höheren Konzentrationen für die Oxidation von Xylit beobachtet; bei Galaktit bleibt die Oxidation auch bei höheren Hydroxyl-Konzentrationen erster Ordnung. Es wird angenommen, daß die Reaktion über einen aktivierten Komplex zwischen [KFe(CN)6]2– und dem Substrat-Anion verläuft; dieser Komplex zerfällt in [KFe(CN)6]3– und ein Substrat-Radikal. Ein möglicher Reaktionsmechanismus wird vorgeschlagen.
  相似文献   

13.
The possibility of using inductively coupled plasma atomic emission spectrometry (ICP-AES) to determine the elemental composition of archaeological bones elements was evaluated and discussed. The interferences of the major elements (Ca, P, K, Na, Al and Fe) on the microelements (Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn) were investigated and the appropriate analytical lines were selected. The role of different nebulizers (cross-flow, Babington and Meinhard) on detection limits were investigated. The applicability of the proposed procedure was demonstrated analyzing IAEA-SRM-H-5 (Animal bone); and authentic bone sample dating back to the 4th century BC. These results were compared to ETAAS and ICP-MS.  相似文献   

14.
The extraction process of ternary ion-association complexes of molybdenum (VI) with some polyphenols (4-nitrocatechol, 2,3-dihydroxy naphthalene) and thiazolyl blue has been investigated by using an extraction-spectrophotometric method. The optimum conditions for their quantitative preparation in aqueous medium and subsequent extraction into an organic solvent have been found. The extraction, distribution and association constants, and the recovery factors have been calculated. The composition of the complexes has been determined. A precise, sensitive and simple extraction-spectrophotometric method for determination of molybdenum in products from ferrous metallurgy has been developed.  相似文献   

15.
Formation of molecular complexes betweenDDT as acceptor and indole, 2-methylindole, 3-methylindole, benzene and naphthalene as donors have been studied in carbon tetrachloride using refractometric and differential refractometric measurements. Titration techniques through these measurements have indicated11 stoichiometry of these complexes. Equilibrium constants (K 1) and extent of electronic polarization were calculated. Two types of complexes were observed, one association involving primarily the benzhydryltrichloromethyl grouping ofDDT with a polar complexing agents, and the other interaction of theDDT aromatic -electron system with -electrons of donors in the complexing molecule. These data support the charge-transfer complex formation hypothesis for the mode of action ofDDT on molecular level.
Refraktometrische Untersuchungen an Molekülkomplexen von DDT mit einigen biologisch relevanten Verbindungen
Zusammenfassung Es wurde die Bildung von Molekülkomplexen zwischenDDT als Acceptor und Indol, 2-Methyl-indol, 3-Methyl-indol, Benzol und Naphthalin als Donor in CCl4 mittels Refraktometrie und differenzieller Refraktometrie untersucht. Es wurde11-Stöchiometrie der Komplexe festgestellt, Gleichgewichtskonstanten und das Ausmaß der Elektronenpolarisation wurden berechnet. Zwei Typen von Komplexen wurden beobachtet; in einem Fall erfolgt die Assoziation primär über die Benzhydryltrichlormethyl-Gruppierung desDDT, im anderen Fall über -Elektronenwechselwirkungen. Die Daten unterstützen ein chargetransfer-Modell der Komplexbildung vonDDT mit geeigneten Donormolekülen.
  相似文献   

16.
The molecular complexation ofDDT (acceptor) with some compounds of biological interest as donors (e.g. indole, 2-methylindole, 3-methylindole, benzene and naphthalene) have been studied using refractive index,Guggenheim and dielectric titration plot methods. The interaction between these donors with solvents (CCl4 and C6H6) have also been observed by calculating ind through ind=solinert. These data have shown that the molecular interaction between polar solutes and non-polar aromatics is governed by dipole-induced dipole electrostatic attraction. The dipole moment obtained due to charge transfer (DA) has also been calculated and found that its value increases with the increase in the extent of interaction between donor and acceptor. These data support the charge-transfer complex formation hypothesis for the mode of action ofDDT on molecular level.
Dielektrizitäts-Untersuchungen an Molekülkomplexen von DDT mit einigen biologisch relevanten Verbindungen
Zusammenfassung Es wurden Molekülkomplexe vonDDT (als Acceptor) mit einigen Verbindungen von biologischem Interesse (als Donoren: Indol, 2-Methyl-indol, 3-Methyl-indol, Benzol und Naphthalin) mittels Brechungsindex,Guggenheim-Methode und dielektrischer Titration untersucht. Dipolmomentberechnungen ergaben, daß die intermolekulare Wechselwirkung von einer Anziehung induzierter Dipol-Dipol bestimmt wird; es wurde auch der charge-transfer-Anteil des Dipolmoments abgeschätzt. Alle diese Daten unterstützen die Annahme der charge-transfer-Komplexierung vonDDT.
  相似文献   

17.
Summary Previous structure-activity studies of captopril and related active angiotensin-converting enzyme (ACE) inhibitors have led to the conclusion that the basic structural requirements for inhibition of ACE involve (a) a terminal carboxyl group; (b) an amido carbonyl group; and (c) different types of effective zinc (Zn) ligand functional groups. Such structural requirements common to a set of compounds acting at the same receptor have been used to define a pharmacophoric pattern of atoms or groups of atoms mutually oriented in space that is necessary for ACE inhibition from a stereochemical point of view. A unique pharmacophore model (within the resolution of approximately 0.15 Å) was observed using a method for systematic search of the conformational hyperspace available to the 28 structurally different molecules under study. The method does not assume a common molecular framework, and, therefore, allows comparison of different compounds that is independent of their absolute orientation.Consequently, by placing the carboxyl binding group, the binding site for amido carbonyl, and the Zn atom site in positions determined by ideal binding geometry with the inhibitors' functional groups, it was possible to clearly specify a geometry for the active site of ACE.  相似文献   

18.
An attempt was made to study the oxidation of manganese by air in synthetic waters. A series of batch experments were performed at differnet values of concentration, temperature and pH. Unoxidized manganese in the solution was determined by formaldoxime spectrometric method. Results of these studies indicated that the air oxidation of manganese soluble in water can be effectively performed in basic media and that oxidation yield increasedwith an increase in pH and concentration. The yield was very high in the presence of manganese dioxide, sepiolite or clinoptilolite in solution and, the oxidation was almost completed especially at high values of pH and concentration. The reaction was found to be first order with respect to Mn2+ with a very low activation energy. A yield of 62% was obtained for the air oxidation of wastewater taken from the treatment plant of Corum Municipality.  相似文献   

19.
Sonolysis of aqueous solution of chlorobenzene at 200 kHz frequency in the presence of transition metals chlorides was investigated. Through analyzing the nature and distribution of the products detected in the reaction mixture, a new mechanism of sonodegradation is advanced. Depending on the metals used and their behavior during sonolysis, we were able to discriminate between inside and outside cavitation bubble mechanisms. Iron and cobalt chlorides, which could undergo redox reactions in the presence of HO radicals generated ultrasonically, give higher amounts of phenolic compounds compared with palladium chloride that undergoes a reduction to metal. Palladium reduction takes place in bulk solution and therefore all organic reactions that compete for hydrogen must occur also in bulk solution. Accordingly, palladium can be a useful tool in determining the reaction site and the decomposition mechanism of organic compounds under ultrasonic irradiation.  相似文献   

20.
The N-acyliminium intermediates of 3,4-dihydroisoquinoline and salts of isoquinoline with acyl chlorides were successfully used as amidoalkylating reagents toward synthesis of heterocyclic aromatics as indole, pyrrole, thiophene and pyrazine.  相似文献   

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