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1.
Interaction of quantum system S a described by the generalised × eigenvalue equation A| s =E s S a | s (s=1,...,) with quantum system S b described by the generalised n×n eigenvalue equation B| i = i S b | i (i=1,...,n) is considered. With the system S a is associated -dimensional space X a and with the system S b is associated an n-dimensional space X n b that is orthogonal to X a . Combined system S is described by the generalised (+n)×(+n) eigenvalue equation [A+B+V]| k = k [S a +S b +P]| k (k=1,...,n+) where operators V and P represent interaction between those two systems. All operators are Hermitian, while operators S a ,S b and S=S a +S b +P are, in addition, positive definite. It is shown that each eigenvalue k i of the combined system is the eigenvalue of the × eigenvalue equation . Operator in this equation is expressed in terms of the eigenvalues i of the system S b and in terms of matrix elements s |V| i and s |P| i where vectors | s form a base in X a . Eigenstate | k a of this equation is the projection of the eigenstate | k of the combined system on the space X a . Projection | k b of | k on the space X n b is given by | k b =( k S b B)–1(V k P})| k a where ( k S b B)–1 is inverse of ( k S b B) in X n b . Hence, if the solution to the system S b is known, one can obtain all eigenvalues k i } and all the corresponding eigenstates | k of the combined system as a solution of the above × eigenvalue equation that refers to the system S a alone. Slightly more complicated expressions are obtained for the eigenvalues k i } and the corresponding eigenstates, provided such eigenvalues and eigenstates exist.  相似文献   

2.
Crystallization of iron phosphate glasses   总被引:1,自引:0,他引:1  
Differential thermal analysis (DTA), thermogravimetric analysis (TG), X-ray diffraction and Mössbauer spectroscopy were employed in the investigation of crystalline products of FeOx-P2O5 glasses generated by various heat treatments. In glasses with a high value of =Fe2+/(Fe2+ + Fe3+), absorption of oxygen occurs in a broad temperature range identified by TG. Depending on the value of , two exotherms appear in the DTA curves, the low-temperature one corresponding to crystallization of the Fe3(PO4)2 type regions, and the high-temperature one being related to various phases with dominating FePO4. Each exotherm has its own transformation region, identical in absolute value. The Mössbauer spectra of glasses which underwent thermal treatment at higher temperatures exhibit some indication of phases of the types Fe3(PO4)2 · xH2O and FePO4 · xH2O.
Zusammenfassung Differentialthermoanalyse (DTA), thermogravimetrische Analyse (TG), Röntgendiffraktion und Mössbauerspektroskopie wurden bei der Untersuchung (von kristalliner Produkte) durch verschiedene thermische Behandlungen hergestellten FeOx-P2O5 Gläsern eingesetzt. In den Glasarten mit einem hohen Wert von =Fe2+/(Fe2+ + Fe3+) erfolgt die Sauerstoffabsorption in einem durch TG [nachgewiesenen breiten Temperaturbereich. In Abhängigkeit von dem -Wert erscheinen zwei Exothermen in den DTA-Kurven, von denen der bei niedriger Temperatur die Kristallisation des Fe3(PO4)2 entspricht, und jener bei höheren Temperaturen in verschiedenen Phasen dem FePO4. Jede Exotherme hat ihr eigenes Umwandlungsgebiet, das in absolutem Wert identisch ist. Die Mössbauer-Spektren der Gläser welche einer Wärmebehandlung bei höheren Temperaturen unterzogen worden sind, weisen einige Indikationsphasen der Typen Fe3(PO4)2 · xH2O und FePO4 · xH2O auf.

, , FeOx-P2O5, . , =Fe2+/(Fe2++Fe3+) . , - : Fe3(PO4)2, – FePO4. , . , , Fe3(PO4)2 · 2 FePO4 · 2.


The authors thank Mrs. Simonyiová for assistance in the experimental part of these investigations, and Dr. Horváth and Dr. Vondrovic for performing the X-ray and TG analyses.  相似文献   

3.
The kinetics of the ligand exchange in (PPh4)2[Mo(CN)3O(salhy)]. 6H2O (Hsalhy = salicylaldehyde hydrazone) by a solvent molecule and by 2,2-bipyridine (bpy) have been studied in EtOH. For the ligand exchange by a solvent molecule the pseudo-first order rate constant equals k obs = 3.2 (±0.2) × 10–3 s–1 (t=25 °C), H =67 (± 7) kJ mol–1, S =–75 (±23) J mol–1 K–1, while for the exchange by a bpy molecule k obs=3.5 (±0.2) × 10–3 s–1 (t=25 °C), H =56 (±7) KJ mol–1, S = –104 (±8) J mol–1 K–1. It was found, that all reactions proceed via the same mechanism which involves the chelate ring opening cis to the Mo=O bond. The mechanism of the reaction was proposed and was proved by the synthesis of (PPh4)2[Mo(CN)3O(N-pic)]. 2.5H2O (N-pic denotes that the nitrogen of picolinic acid is trans to Mo=O) by ligand exchange in EtOH, while in aqueous solution the O-pic analogue is formed exclusively.  相似文献   

4.
Summary For visual analysis of the density reorganization and distortion, the one-dimensional cut (x, y 0,z 0) and the two-dimensional cut (x, y, z 0) of the three-dimensional electron density difference function (x, y, z) are frequently employed. However, these cut functions do not satisfy any sum rules in contrast to the original difference function (x, y, z). To avoid this difficulty, the use of the marginal electron density functions x (x) and xy (x, y) and their difference functions x (x) and xy (x, y) is proposed. The marginal densities are condensation of the three-dimensional density onto a particular plane or line of our interest, and they satisfy the sum rule (i.e., the conservation of the number of electrons) exactly. Some basic properties of the marginal electron density are clarified for typical diatomic molecular orbitals. An illustrative application is given for the bonding and antibonding processes in the H2 system.  相似文献   

5.
Kinetic equations were formulated, which describe coagulation–fragmentation process in a low concentrated suspension flow at a low shear rate. In such a system dispersed phase divided into fine and coarse fractions as the system is brought to equilibrium. Kinetic equations of two-fraction model were formulated. An approximate solution and, in one particular case, the exact solution of these equations were obtained for the equilibrium state. Detailed analysis of equilibrium particle distribution over the mass m was performed for an exponential coagulation kernel = 0 m and an degenerated disintegration kernel = 12, in which the disintegration frequency is an exponential function of aggregate mass 1 = 0 m + , and the probability of the fragment detachment from an aggregate is independent ofm and decreases exponentially with an increase in mass of a fragment: 2 = 0 –1exp(–/0). The equilibrium distribution was shown to exist only at > 0, and in particular, it is described at = = 1 by the f() = 00 –1exp(–/0) and F(m) = Cx –1(x + 1)2 – 1 e x functions for the particles of fine and coarse fractions (x = m/m 0, = m 0/0, m 0 and 0 are the characteristic masses of coarse and fine fractions, respectively). The particle distribution for the fine fraction at 1 is well approximated by the Gaussian distribution exp[–(mm 0)2/(4–1 m 00)].  相似文献   

6.
The title reaction has been studied spectrophotometrically in aqueous medium as a function of [substrate complex], [ligand], pH and temperature at constant ionic strength. At the physiological pH (7.4) the interaction with azide shows two distinct consecutive steps, i.e., it shows a non-linear dependence on the concentration of N3 ; both processes are [ligand]-dependent. The rate constant for the processes are: k 110–3 s–1 and k 210–5 s–1. The activation parameters calculated from Eyring plots are: H 1 = 14.8 ± 1 kJ mol–1, S 1 = –240 ± 3 J K–1 mol–1, H 2 = 44.0 ± 1.5 kJ mol–1 and S 2 = –190 ± 4 J K–1 mol–1. Based on the kinetic and activation parameters an associative interchange mechanism is proposed for the interaction process. From the temperature dependence of the outersphere association equilibrium constant, the thermodynamic parameters calculated are: H 1 0 = 4.4 ± 0.9 kJ mol–1, S 1 0 = 64 ± 3 J K–1 mol–1 and H 2 0 = 14.2 ± 2.9 kJ mol–1, S 2 0 = 90 ± 9 J K–1 mol–1, which gives a negative G 0 value at all temperatures studied, supporting the spontaneous formation of an outersphere association complex.  相似文献   

7.
The activity and activity coefficients of the components of the NaNO2-KNO3 system, determined from the experimental data on the saturated vapor pressure at 798, 823, and 848 K, are used to calculate the relative and excess partial molar Gibbs energies (G i and G i e x c), entropies (S i and S i e x c), and integral relative and excess thermodynamic functions (G, G e x c, S, and S e x c) of the system.  相似文献   

8.
Correlated measurement of the lifetime and of the lineshape of the 511 keV annihilation radiation of positrons (age-momentum correlation, AMOC) has become a powerful tool for investigating reactions of positron or positronium in condensed matter as a function of time. The beam-based + AMOC method installed at the Stuttgart relativistic positron beam facility (E kin e+ 4MeV) offers substantial advantages over the conventional E coincidence technique resulting in a fast data taking due to the unity detection efficiency of the + scintillator which provides the start signal for the lifetime measurement. In this paper the application of AMOC to positronium chemistry is illustrated by the study of spin conversion of positronium in the system methanol/HTEMPO as a function of HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, a paramagnetic solute) concentration. The same technique can be applied to other systems and other reactions in positronium chemistry, e. g., oxidation or complex formation.  相似文献   

9.
Summary Qualitative molecular orbital considerations of the complexes [5-CPV(CO)3 L] (L = substituted phosphane, SbPh3, AsPh3, CN) suggest that s' V chemical shift parameters () obtained for these compounds should correlate with the -acceptor abilities of L. Based on observed r-values, the ligands are arranged in sequence of their -acceptor ability, which lies in the order P(OR)3 > CN > PR'33 SbPh3 PPhF2 > P(i-Bu)3 P(NR 2 )3 > PPh3 > AsPh3 Nuclear spin-spin coupling constants J (51V-31 P), line widths H and i.r. data in the (CO) region are also presented.P(OR)3 = P(OEt)3, 4-Ethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]-octane; R = Me, n-Pr; R = Me, Et.  相似文献   

10.
When heated, the 3-hydroxybenzoates of Y, Sm and Eu(III) decompose in two steps. The hydrates first lose crystallization water and the anhydrous complexes are then transformed to oxides in air, and to mixtures of oxide and C in nitrogen atmosphere. When heated in air, the pentahydrates of La, Pr and Nd are dehydrated in two stages and the anhydrous complexes are then transformed to oxides; when heated in nitrogen, they are dehydrated in one step and then decomposed to mixtures of oxides and C.
Zusammenfassung Die 3-Hydroxybenzoate von Y, Sm und Eu(III) zersetzen sich beim Erhitzen in zwei Schritten. Die Hydrate verlieren zunächst Kristallwasser und die wasserfreien Komplexe werden in Luft in die Oxide und in Stickstoffatmosphäre in ein Gemisch des betreffenden Oxids und Kohlenstoff überführt. Beim Erhitzen in Luft werden die Pentahydrate von La, Pr und Nd in zwei Schritten dehydratisiert und die wasserfreien Komplexe in die Oxide überführt; beim Erhitzen in Stickstoff erfolgt dagegen die Dehydratisierung in nur einem Schritt und Endprodukt der Zersetzung ist ein Gemisch von Kohlenstoff und dem entsprechenden Oxid.

3- , . , — . , . , .
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11.
New active and selective catalysts were prepared by adding different quantities of Te to CdMoO4. These were already selective at low Te levels, but the one with a Cd/Te/Mo ratio of 1/1/1 was specific for butadiene. The catalytic behavior of the Cd–Te–Mo–O system has been correlated mainly with the CdTeMoO6 phase in the region rich in Te and with the CdMoO4 phase with Te as dopant in the region poor in Te.
Te CdMoO4. Te, CdTeMo=111 . Cd–Te–Mo–O CdTeMoO6 Te, CdMoO4 Te , Te.
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12.
The thermal decomposition of Cu(I) phosphine complexes of the general types (CuXPPh3)4, [CuX(PPh3)2] and [CuX(PPh3)3] was investigated.The thermal decomposition of (CuXPPh3)4, where X denotes Cl, Br, I, NO 3 and PPh3=P(C6H5)3, occurs with formation of a phosphine oxide intermediate. For the remaining complexes this intermediate was not proved in the thermal decomposition.
Zusammenfassung Die thermische Zersetzung der Cu(I)-Phosphinkomplexe vom allgemeinen Typ (CuXPPh3)4 und [CuX(PPh3)2], wie auch [CuX(PPh3)3] wurde untersucht. Die thermische Zersetzung von (CuXPPh3)4, wobei X=Cl, Br, I und NO 3 bedeutet und PPh3=P(C6H5)3, verläuft unter Bildung eines Phosphinoxid Zwischenproduktes, bei den übrigen Komplexen konnte dieses im Laufe der thermischen Zersetzung nicht nachgewiesen werden.

Résumé On a étudié la décomposition thermique des complexes phosphine-Cu(I) de formule générale (CuXPPh3)4, [CuX(PPh3)2], [CuX(PPh3)3]. La décomposition thermique de (CuXPPh3)4, où X désigne Cl, Br, I et NO 3 , et PPh3=P(C6H5)3, s'effectue avec formation d'un oxyde de phosphine intermédiaire; avec les autres complexes, cet intermédiaire n'a pas été mis en évidence au cours de la décomposition thermique.

(CuXPPb3)4 [CuX(PPh3)2] [CuX(PPh3)3]. (CuXPPh3)4, X=Cl, Br, I, NO 3 , PPh3=(65)3 . .
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13.
The kinetics and mechanism of redox reactions of U3+ ions with 2-chloro and 2-bromopropanoic acids were studied. The influence of pH led to the determination of the rate constants corresponding to two parallel steps. The influence of binary mixtures on the reaction rate was followed. The kinetic results for halogen-substituted carboxylic acids forming an isokinetic series have been compared.
U+3 2-- 2- . pH . . , .
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14.
Silanes of the type R1R2Si(H)CH2OEl(O)xR y 3 [R=organyl; El=C (x=y=1), S (x=2,y=1), P (x=1y=2)] undergo a thermally induced rearrangement to give silanes of the type R1R2Si (CH3)OEl(O)xR y 3 . The energetic (reaction enthalpy) and kinetic data (reaction order, enthalpy and entropy of activation) of this reaction were determined by means of differential scanning calorimetry. The results obtained are discussed in terms of mechanistic aspects.
Zusammenfassung Silane des Typs R1R2Si(H)CH2OE10xR y 3 mit R=organyl; E1=C (x=y=1), S(x=2, y=1) oder P (x=1,y=2) zeigen eine thermisch induzierte Umlagerung zu Silanen des Typs R1R2Si(CH3)OE10xR y 3 . Energetische (Reaktionsenthalpie) und kinetische Daten (Reaktionsordnung, Aktivierungsenthalpie und -entropie) dieser Umlagerungsreaktion wurden mittels DSC ermittelt. Die mechanistischen Aspekte der Ergebnisse werden diskutiert.

R1R2Si(H)OE1(O)xR y 3 , R= , E1=C (x=y=1), S (x=2,y=1), P (x=1,y=2), R1R2Si(CH3)OE1(O)xR y 3 . ( ) ( , ) . .

  相似文献   

15.
Thermal characteristics of the vanadates of zinc, manganese and silver have been studied by DTA and TG techniques and the different transition products thus obtained have been characterised by IR, X-ray diffraction and magnetic susceptibility data. Chemical analyses indicate the following compositions of these vanadates: (1) Zn2V2O7.5H2O, (2) Zn3(VO4)2.3H2O, (3) Mn(VO3)2.2H2O and (4) Ag3VO4. The DTA curves indicate that zinc pyrovanadate undergoes endothermic changes at 110–195, 265, 365, 440, 660° and one exothermic change at 485°. This system is diamagnetic which becomes completely paramagnetic after 660°. Zinc orthovanadate exhibits a number of endothermic peaks at 300, 470, 700, 815 and 930° respectively. This system is feebly paramagnetic and retains this property up to 930°. Manganese metavanadate undergoes endothermic changes at 240, 280–590, 830 and 880° respectively. This vanadate is paramagnetic and paramagnetism increases appreciably at 590° and remains constant up 830°. Silver orthovanadate exhibits three endothermic changes at 180, 455 and 640°, respectively.
Zusammenfassung Die thermischen Charakteristika der Vanadate von Zink, Mangan und Silber wurden durch DTA- und TG-Methoden untersucht und die auf diese Weise erhaltenen verschiedenen Übergangsprodukte durch Daten aus IR-, Röntgen- und magnetischer Susceptibilität charakterisiert. Die chemische Analyse deutet auf folgende Zusammensetzung dieser Vanadate: 1) Zn2V2O7.5H2O, 2) Zn3(VO4)2.3H2O, 3) Mn(VO3)2.2H2O und 4) Ag3VO4. Die DTA-Kurven zeigen endotherme Veränderungen des Zink-pyrovanadats bei 110–195, 265, 365, 440 und 660° und eine exotherme Veränderung bei 485°. Dieses System ist diamagnetisch und wird nach 660° vollständig paramagnetisch. Zink-orthovanadat zeigt eine Anzahl exothermer Peaks bei 300, 470, 700, 815, bzw. 930°. Dieses System ist schwach paramagnetisch und behält diese Eigenschaft bis zu 930°. Im Manganmetavanadat vollziehen sich endotherme Veränderungen bei 240, 280–590, 830 und 880°. Dieses Vanadat is paramagnetisch, der Pararnagnetismus steigt zusehends bei 590° und bleibt bis zu 830° konstant. Silberorthovanadat zeigt drei endotherme Veränderungen bei 180, 455 bzw. 640°.

Résumé On a étudié par ATD et TG les caractéristiques thermiques des vanadates de zinc, de manganèse et d'argent. La caractérisation des divers produits de transition ainsi obtenus a été effectuée à partir des données fournies par IR, rayons X et susceptibilité magnétique. Les analyses chimiques indiquent les compositions suivantes de ces vanadates: (1) Zn2V2O7.5H2O, (2) Zn3(VO4)2.3H2O, (3) Mn(VO3)2.2H2O et (4) Ag3VO4. Les courbes ATD du pyrovanadate de zinc montrent des effets endothermiques à 110–195, 265, 365, 440 et 660° ainsi qu'un phénomène exothermique à 485°. Ce corps est diamagnétique; il devient complètement paramagnétique au-dessus de 660°. L'orthovanadate de zinc donne des pics endothermiques à 300, 470, 700, 815 et 930°. Il est faiblement paramagnétique jusqu'à 930°. Le métavanadate de manganèse est le siège de phénomènes endothermiques à 240, 280–590, 830 et 880°. Il est paramagnétique et son paramagnétisme augmente de manière appréciable à 590° pour rester constant jusqu'à 830°. L'orthovanadate d'argent montre trois effets endothermiques à 180, 455 et 640°.

, . - , . : Zn2V2O7·5H2O, Zn3(VO4)2 · 3H2O, Mn(VO3)2· 2H2O Ag3VO4. , 110–195°, 265, 365,440 660° 485°. , 660° . 300, 470, 700, 815 930°. 930°. 240, 280–590, 830 880°. , 590° 830°. 180, 455 640°.


The authors are grateful to the Physical Research Wing and Catalyst Research and Development Section, F. C. I., Sindri and also the Analytical Physics Division and Catalyst Section, I.I.P., Dehradun (India) for their help in getting TG and X-ray patterns of the catalysts studied.  相似文献   

16.
The rate of methane formation on zinc-chromium catalysts is described by zero-order rate law, If the catalyst is activated by copper, the rate of methane formation increases due to a decrease in the activation energy of the reaction. Presumably the formation of methane and methanol takes place on different active centers.
, . , . , .
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17.
One method which has been used in the literature to determine the eigenvalues F k (0) of a hamiltonian operator = + W ( = kinetic energy operator) is to apply an approximation scheme (e.g. variational method) to the operator R () = + V + (W – V) with eigenvalues G k (), where the eigenvalue problem associated with (o) = + V is solvable. Specifically, F k (0) = G k (1). We investigate the method from a perturbation theoretic viewpoint. There is a renormalization map R:, [0, 1], [0, ), which relates the G() to the eigenvalues E() of () = + V + W. This, in turn, implies a linear relationship between the Rayleigh-Schrödinger -series coefficients G (n) and the -series coefficients E (n) of the form G=CE, where C is an infinite lower-triangular matrix. The renormalized -series, 01, is useful in the accurate computation of F (0) as well as the eigenvalues E(), 0< . In standard cases, the -series is Borel summable to G(). Applications are made to anharmonic oscillators and hydrogen atoms in radial fields.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday  相似文献   

18.
The treatment of Fe(III)NaY zeolite with NaCl solution does not lead to a back-exchange of ferric species but the cationic Fe rearranges into new complexes which are more deeply reduced by hydrogen and less self-reduced by vacuum heat treatment than the parent Fe species in FeNaY zeolite.
Fe(III)NaY NaCl . , Fe , , , Fe FeNaY.
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19.
Studies of the effect of zinc chloride and aluminium additives on the activity of a Pd/Al2O3 catalyst (5 wt.%Pd) in the isomerization of heptene-1, allylbenzene,p-allylphenol and 4-allyl-2-methoxyphenol (eugenol) indicate that the rate and selectivity of isomerization depend on the sequence of addition of salts and reagent to the catalytic system. The simultaneous addition of ZnCl2 or AlCl3 with olefin, produces a 2–3 fold increase in the isomer yield compared to ethanol.
Pd/Al2O3- (5 .% Pd) -1, , -, 4--2- (). , . ZnCl2 AlCl3 2–3 .
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20.
A method has been developed that allows the deconvolution of up to 15 overlapping solidstate reactions without previous assumptions. Both the kinetic parameters and the reaction mechanisms fitted by the unit reactions can be determined from a series of non-isothermal experiments carried out at different heating rates.
Zusammenfassung Es wurde eine methode zur Dekonvolution von bis zu 15 einander überlappenden Festphasenreaktionen entwickelt, die keinerlei vorherige Annahmen notwendig macht. Mittels einer Reihe nichtisothermer Experimente mit unterschiedlichen Aufheizgeschwindigkeiten können sowohl die kinetischen Parameter als auch der Reaktionsmechanismus der Teilreaktionen bestimmt werden.

, 15. .
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