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1.
The correlations between the values of the lgK (K = stability constant of the lanthanide complex) and the reciprocal of the ionic radius 1/r or the sum of the ionization potentials 1 3 I for the lanthanide ions were reviewed for different ligands. A straight-line relationship (lgK – lgK)/lgK vs. (1/r – 1/r)/(1/r) or vs. ( 1 3 I1 3 I)/ 1 3 I was found within the tetrads La-Nd, Gd-Ho, and Er-Lu.
Bemerkungen zum periodischen Wechsel der Stabilitätskonstanten von Lanthaniden-Komplexen
Zusammenfassung Es wurde eine Übersicht der Korrelationen zwischen den Werten von logK (K = Stabilitätskonstante der Lanthanidenkomplexe) und den reziproken Ionenradien 1/r oder der Summe der Ionisierungspotentiale 1 3 I für die Lanthanidenionen für verschiedene Liganden gegeben. Dabei wurde eine lineare Korrelation für (lgK – lgK)/lgK gegen (1/r – 1/r)/(1/r) oder gegen ( 1 3 I1 3 I)/1/3 I innerhalb der Tetraden La-Nd, Gd-Ho und Er-Lu aufgefunden.
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2.
Alkoxy-derived cordierite gels were synthesized from tetraethylorthosilicate (TEOS), aluminum isopropoxide (Al(OPr i )3), and magnesium ethoxide (Mg(OEt)2). TEOS was partially hydrolyzed at molar ratios H2O/TEOS = 1.2, in the presence of hydrochloric acid as a catalyst, HCl/TEOS = 0.1. Aluminum and magnesium alkoxides were added successively or as a double alkoxide. Phase transformations occurring in the gel were studied by differential thermal analysis, x-ray diffractometry, and Fourier-transform infrared spectroscopy. In all cases, -cordierite crystallized at similar temperatures (950–1000°C) with small amounts of spinel, which confirms dominant influence of the optimal conditions for partial hydrolysis of TEOS on the gels homogeneity. The transformation of - into -cordierite began at about 1100°C. Broadening of diffraction peaks and appearance of new bands in the FT IR spectra confirmed the transformation of - into modulated -cordierite at temperatures above 1300°C. Differential thermal analysis under nonisothermal conditions also proved homogeneous nucleation with constant rate and three-dimensional crystallite growth during -cordierite crystallization. The overall activation energy of the crystallization of -cordierite is 580 ± 81 kJ/mol.  相似文献   

3.
A mechanism is proposed for the radiolysis of adsorbed N2O describing the experimental dependences of the radiation-chemical yields of O st and N2 on N2O coverages.
N2O, - O st N2 N2O.
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4.
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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5.
Conclusions From the roots ofXanthogalum purpurascens growing in the Transcaucasus, we have isolated a new coumarin, C24H26O7 with mp 111–113°C, [] D 20 –164.2° (c 0.97; ethanol) which we have called xanthalin. On the basis of the NMR spectrum it has been established that xanthalin is 3, 4-diangeloyl-2, 2-dimethyl-3, 4-dihydropyrano-5, 6:6, 7-coumarin.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 5, pp. 280–283, 1968  相似文献   

6.
The apparent molar heat capacity, C p,, of aqueous NaOH has been measured at temperatures between 50 and 250°C and molalities from 0.05 to 1.5 mol-kg–1. Enthalpies of dilution L were also determined at 99°C and apparent molar relative enthalpies L were calculated up to 1.9 m. Measurements were performed by means of a flow calorimetric apparatus constructed in our laboratory and standardized for C p, and L with aqueous Na2SO4 and with the formation of water from its ions, respectively. Characteristics and performance of this calorimeter are described in detail. Pitzer's semiempirical equations are used for the representation of the results and a general fitting of C p, data is reported using also recent literature values measured between 4 and 55°C. The fitted parameters are finally utilized, through an integration procedure, to derive a general equation to calculate L at any temperature between 4 and 250°C.  相似文献   

7.
The desorption of H2 from clean and CO-poisoned Pd wires was studied by a temperature programmed desorption technique. Poisoning effect of CO on H2 desorption process can be accounted for in terms of blockage of the surface sites for the recombination of H atoms.
H2 , CO, - . CO H2 , , , .
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8.
Dysprosium molybdate, Dy2(MoO4)3, displays a ferroelectric phase transition at 145 °C. The X-ray and thermal (DTA, TG and DSC) properties of this compound have been studied. The X-ray study confirmed the ferroelectric phase in the orthorhombic space group Pba2. Thermal analysis demonstrated the existence of a ferroelectric and another phase transition in this compound.
Zusammenfassung Dysprosiummolybdat, Dy2(MoO4)3 (Abk.: DMO), ein Vertreter der Seltener-denmolybdatreihe zeigt bei 145 °C einen ferroelektrischen Phasenübergang. Röntgendiffraktion und thermische Eigenschaften (DTA, TG, DSC) der genannten Verbindung wurden untersucht. Auf Grund der Röntgendiffraktionsuntersuchung gehört die ferroelektrische Phase in die orthorhombische Raumgruppe Pba2. Mittels Thermoanalyse konnte bei dieser Verbindung die Existenz ferroelektrischer und anderer Phasenübergänge nachgewiesen werden.

145 °C. (, ) . , Pba2. .


The authors wish to thank Prof. A. Paul and Mr. R. Bhatnagar for their kind help in some of the experimental work. One of us (MR) gratefully acknowledges a Fellowship from DST, Government of India.  相似文献   

9.
Zusammenfassung Das Verbrennen von Mischungen der exothermen Systeme Al-NaF-NaNO3 und Al-CaF2-NaNO3 wurde durch Röntgenanalyse ergänzte DTA untersucht. Um den Einfluß des durch Dissoziation von NaNO3 gebildeten Sauerstoffs zu bestimmen wurden auch Mischungen, welche anstatt NaNO3 NaNO2 oder Na2O2 enthielten, geprüft.Zwei, bei 310° bzw. 850° einsetzende exotherme Reaktionen wurden in den Gemischen vom Typ Al-NaF-NaNO3 gefunden. Die erste ist der Dissoziation von NaNO3 zuzuschreiben, die zweite ist der Anwesenheit von Luft zuzuordnen.Beide exothermen Reaktionen wurden im System Al-CaF2-NaNO3 in Richtung höherer Temperaturen verschoben. Die Untersuchung der NaNO2- oder Na2O2-haltigen Gemische anstatt NaNO3 zeigte, daß die Dissoziation von NaNO3 den zum Verbrennen benötigten Sauerstoff liefert, andererseits würde letztere Reaktion sonst nur in begrenztem Ausmaß stattfinden.
Combustion of exothermic mixtures belonging to the system Al-NaF-NaNO3 and Al-CaF2-NaNO3 was investigated by DTA and X-ray analysis. In order to determine the influence of the oxygen generated by dissociation of NaNO3, the mixtures containing NaNO2 or Na2O2 instead of NaNO3 were also examined.Two exothermic reactions starting at 310° and 850° rsp. were found in the mixtures of the Al-NaF-NaNO3 type. The first is due to the dissociation of NaNO3 and the second proceeds independence of the availability of air.Both exothermic reactions were shifted to higher temperatures in the system Al-CaF2-NaNO3. Investigation of the mixtures containing NaNO2 or Na2O2 instead of NaNO3 has proved that the dissociation of NaNO3 supplies the oxygen required for combustion which should otherwise proceed only in a limited extent.

Résumé On a étudié, par ATD et par analyse aux rayons X, la combustion des mélanges exothermiques appartenant aux systèmes Al-NaF-NaNO3 et Al-CaF2-NaNO3. Afin de déterminer l'influence de l'oxygène engendré par la dissociation de NaNO3, on a étudié de même des mélanges contenant NaNO2 ou Na2O2 au lieu de NaNO3.On a trouvé, dans les mélanges du type Al-NaF-NaNO3, des réactions exothermiques à partir des temperatures respectives de 310° et 850°. La première est due à la dissociation de NaNO3 et la seconde dépend de l'air disponible.Dans le système Al-CaF2-NaNO3 les deux réactions sont déplacées vers les températures plus élevées. L'examen de mélanges contenant NaNO2 ou Na2O2 au lieu de NaNO3 à montré que c'est la dissociation de NaNO3 qui fournit l'oxygène nécessaire pour la combustion. Celleci n'aurait lieu, autrement, que d'une manière limitée.

, l-NaF-NaNO3 Al-CaF2-NaNO3. , NaNO3, , NaNO3, , NaNO2 Na2. , Al-NaF-NaNO3 , 310° 850°. , . Al-CaF2-NaNO3 . , NaNO2 Na2O2, , , , , .
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10.
From a methanolic extract of the epigeal part ofRhinopetalum stenantherum have been isolated -chaconine (I) and the new glucoalkaloids stenanthine with mp 262–264°C []D 46.5°, C45H73NO15 (II), and stenanthidine with mp 269–271°C, []D –47.5°, C39H63NO11 (III). On the basis of the facts that partial hydrolysis of the trioside (II) formed the biosides (I) and (III), and that on the hydrolysis of the latter the monoside -chaconine was found, it may be assumed that stenanthine has the structure of solanidine 3-0-{[0--D-glucosyl-(1 6)]-[0--L-rhamnosyl-(1 4)]-D-glucoside}, and stenanthidine that of solanidine 3-0-[0--D-glucosyl-(1 6)-D-glucoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 349–356, May–June, 1981.  相似文献   

11.
Conclusions 1. Xanthalin has been shown to have the structure of 2, 2-dimethyl-3, 4,-diangeloyloxy-3, 4-dihydropyrano-5, 6:6, 7-coumarin on the basis of the preparation of a number of derivatives and cleavage products.2. The following products of the alkaline hydrolysis of xanthalin have been isolated and characterized for the first time: (±)-3, 4-dihydroxy-3, 4-dihydroxanthyletin (isokhellactone), C14H14O5, with mp 213–215° C and (–)-trans-3-hydroxy-4-methoxy-3, 4-dihydroxanthyletin (isomethylkhellactone, C15H16O5, with mp 136.5–138° C and [] D 20 –47.7 (ethanol).Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 14–19, 1970  相似文献   

12.
Transparent and porous boehmite, -Al2O3 (500°C) and -Al2O3 (900° and 1000°C) thin sheets (50–100 m) have been prepared from boehmite sols. -Al2O3 shows about 48% porosity and 292 m2/g surface area. On transformation from -Al2O3 (500°C) to -Al2O3 (900°C), the porosity still remains high, i.e. 45%; however, the surface area becomes 138 m2/g. The porosity and surface area of -Al2O3 become about 41% and 97 m2/g respectively on further heating to 1000°C. A gradual increase of average pore radius during this thermal treatment suggests that coarsening of the pore occurred during the densification process. Both -Al2O3 and -Al2O3 show high degree of transmission from UV to NIR wavelength region. Cerium exists in +4 oxidation state in the boehmite as well as in the - and -Al2O3. The ultraviolet absorption edge of the alumina was tailored by varying the concentration of cerium.  相似文献   

13.
    
On the basis of our own results and literature data it is concluded thatvC=C and the stability of surface -complexes of olefins with transition metal ions are governed by the nature of metal and its valence state.
, C=C - .
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14.
Zusammenfassung Für die im Plasma an Albumin gebundenen sog. freien Fettsäuren (FFS) wird ein neues gas-chromatographisches Analysenverfahren vorgestellt. Das Probenvolumen beträgt 50 l Serum oder Plasma. Die Extraktion erfolgt in 1,1 ml CHCl3/CH3OH (21, v/v) mit n-Heptadecansäure als innerem Standard (0,05 Val C170/ml). Nach Eindampfen am Rotationsverdampfer werden die FFS im verschlossenen Reaktionskölbchen mit 20 l CH3J/Essigsäureäthylester (11, v/v) über festem K2CO3 bei 90°C 1 h verestert. Die Varianz des Verfahrens errechnet sich bei 15 Parallelbestimmungen zu 4,85%.Vortrag anläßlich der Tagung Spurenanalyse, 2. bis 5. April 1973 in Erlangen.  相似文献   

15.
Effect of thermal pretreatment of chromia-supported iridium catalyst on hydrogen adsorption was studied. It was found that the hydrogen uptake by Ir/Cr2O3 was highly dependent on the reduction temperature. The catalyst proved to be resistant to sintering in oxygen atmosphere at temperatures up to 700 °C and it showed symptoms of redispersion even at 650 °C.
. Ir/Cr2O3 . 700°C, , 650°C .
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16.
Summary The thermal decomposition of [CoCl2(-pic)2] was investigated over the 108°C to 222°C range and the Intennediates CoCl2(-pic) (s) and CoCl2 (s) were observed, with the evolution of (-pic) (g). Quantitative thermodynamic and kinetic data were obtained by performing dynamic and isothermal studies on the complex Additional thermodynamic data were obtained by studying the CoCl2/-pic system in acetone. The effect of the methylsubstituent on the metal-donor-N bond as well as on the thermodynamic quantities were discussed.  相似文献   

17.
On the basis of the thermal investigation of MpynX z mixed complexes (where M=Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+; py=pyridine; or-, - and-picoline; X=Cl, Br, I, OCN, SCN, NO 3 , SO 4 2– ; andn=2,3,4,6;z=1,2), factors influencing the stability of the metal-pyridine-N bond have been determined.On the basis of the measured magnetic susceptibilities the symmetry of the coordina tion sphere of the central atom has been established in the intermediate products formed by the thermal decomposition of cobalt(II) complexes.
Zusammenfassung Aufgrund derivatographischer Untersuchungen von Mischkomplexen des Typs MpynXz (M=Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+; py=Pyridin,, und Piccolin; X=Cl, Br, I, OCN, SCN, NO 3 , SO 4 2– ;n=2, 3, 4, 6;z=1, 2) wurden die die StabilitÄt der Metall-Pyridin-N Bindung beeinflussenden Faktoren geprüft. Durch Messung der magnetischen SuszeptibilitÄten wurde die Symmetrie der KoordinationssphÄre des Zentralatoms des bei der thermischen Zersetzung entstehenden Kobalt(II)-komplexes ermittelt.

Résumé On a examiné des complexes du type Mpy n X z (où M=Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+; py=pyridine,-,- et-piccoline; X=Cl, Br, I, OCN, SCN, NO 3 , SO 4 2– ;n=2, 3, 4, 6;z=1, 2) dans le but de déterminer les facteurs ayant une influence sur la stabilité de la liaison métal-pyridine-N. Par mesure des susceptibilités magnétiques, on a pu établir dans la cas des complexes du Co2+ la sphère de coordination de l'atome central pour les phases intermédiaires produites par décomposition thermique.

nz ( M=n2+, 2+, Ni2+, Cu2+, Zn2+, Cd2+; py= , , ; X=Cl, Br, I, OCN, SCN, NO3 , SO 4 2– ; n=2, 3, 4, 6; z=1, 2) , --N. , (II).


Previous paper of the series: G. Liptay, K. Burger, E. Papp Molnár, Sz. Szebeni, F. Ruff: J. Inorg. Nucl. Chem. 31 (1969) 2359.

We are indebted to Miss é. Szabó for technical assistance.  相似文献   

18.
Hydrogen adsorption on Os-black has been studied by the TPD method in the range from –85 to 450°C. Energetic inhomogeneity of hydrogen chemisorbed at adsorption temperatures of 150 to 450°C has been elucidated.
OS (–85)–450°C. , 150 450°C.
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19.
On the basis of relationships derived by Oplatka et al. [1] correlating the derivative of tensile stress with respect to temperature for a polymer strip at constant length, (/T) t , with the derivative of entropy with respect to strip length, (S/l)T, relationships are derived relating the derivation of strip length with respect to temperature under constant tensile stress, (l/T), with the derivative of entropy with respect to tensile load, (S/) T . The developed relationships are applied to evaluate TMA (thermomechanical analysis) measurements performed with asymmetric and homogeneous cellulose acetate membranes where the membrane strips were kept in deionized water. Moreover, TMA measurements were performed with homogeneous CA membranes while maintaining the membrane strips in bathing solutions of different, but in each instance, constant electrolyte concentrationc s (e.g., LiCl, LiNO3, Li2SO4, CaCl2; 0 c s saturation). Under constant tensile stress, , as-cast asymmetric CA membranes, which are kept in deionized water, first elongate with increasing temperature at temperatures up to about 50°C. However, they shrink with a further increase of temperature in the temperature range 50°C up to about 90°C, whereas creeping starts at temperatures beyond 90°C, leading again to an elongation of the strip with a further increase of temperature. The negative apparent coefficient of thermal expansion, existing between 50° to 90°C, is consistent with shrinking phenomena observed with asymmetric CA membranes [2]. In addition, it correlates well with both an entropy decrease with increasing tensile stress at constant strip length and an entropy increase with decreasing strip length at constant tensile stress. Contraction of the strip with increasing temperature at constant tensile load might be due to increasing coil formation of polymer molecules rendered possible by disintegration of joints such as H-bonds between polymer chains. Depending on the electrolyte of the bathing solution and its concentration, homogeneous CA membranes exhibit positive and negative apparent linear coefficients of thermal expansion under constant tensile stress.  相似文献   

20.
Zusammenfassung Auf Grund thermischer und röntgenographischer Unter-suchungen wurde das vollständige Phasendiagramm Ni–Te aufgestellt. Die Anlage für die thermische Analyse wurde teilweise automatisiert, so daß ausgewählte Temperaturintervalle mit einstellbaren Heiz- udn Kühlgeschwindigkeiten periodisch durchlaufen werden konnten. Zwischen Ni und der kub. f. z. Hochtemperaturphase 1 (Nix Te2) liegt ein Eutektikum bei 34 At% Te und 1004,5°C. 1 schmilzt kongruent bei 38 At% Te und 1021,5°C und hat eine maximale Phasenbreite von 37 At% Te (1004,5°C) bis 43,5 At% Te (880°C). Nickelreiches 1 wandelt sich zwischen 796 und 789°C in eine Ordnungsphase 1 um, die bei 37,7 At% Te und 731°C eutektoidisch in Ni und 2 zerfällt. 1 und 1 wandeln sich unterhalb bei 790°C in die tetragonale 2-Phase um, deren maximaler Homogenitätsbereich von 38,8 At% Te (731°C) bis 41 At% Te (775°C) reicht. Bei 42,5 At% Te und 775°C zerfällt 1 eutektoidisch in 2 und 2. Die 2-Phase (NiTe0,85) bildet sich peritektisch bei 880°C und zerfällt bei 690°C nach 2 1 + . Orthorhombisches 1 disproportioniert sich peritektoidisch bei 742,5°C in 2 und 2. 2 bildet bei 873°C und 49,5 At% Te ein Eutektikum mit der -Phase vom NiAs-Typ. hat einen kongruenten Schmelzpunkt von 900,5°C bei 56 At% Te und eine maximale Phasenbreite von 52 At% Te (690°C) bis 66,6 At% Te (448,5°C). Mit Te bildet die -Phase ein entartetes Eutektikum bei 448,5°C. Die Phasen 2, 1 und wurden röntgenographisch verifiziert und die Abhängigkeit der Gitterparameter der -Phase von der Konzentration vermessen.
Transition metal-chalcogene systems, III: The system Ni–Te
Based on thermal and X-ray measurements the complete Ni–Te phase diagram was constructed. The equipment for thermal analysis was partially automated so that selected temperature intervals could be periodically scanned by programmed heating and cooling rates. Between Ni and thefcc high temperature phase 1 (Nix Te2) a eutectic exists at 34 at% Te and 1004.5°C. 1 melts congruently at 38 at% Te and 1004.5°C, and has a maximum phase width from 37 at% Te (1004.5°C) to 43.5 at% Te (880°C). Nickel-rich 1 transforms between 796 and 789°C into an ordered phase 1 which decomposes eutectoidally into Ni and 2 at 37.7 at% Te and 731°C. 1 and 1 transform at temperatures below 790°C into the tetragonal 2-phase which has a maximum range of homogeneity from 38.8 at% Te (731°C) to 41 at% Te (775°C). At 42.5 at% Te and 775°C 1 decomposes eutectoidally into 2 and 2. The 2-phase (NiTe0.85) is formed by the peritectic reactionL + 1 2 at 880°C and decomposes at 690°C according to 2 1 + . Orthorhombic 1 disproportionates peritectoidally at 742.5°C into 2 and 2. 2 forms at 873°C and 49.5 at% Te a eutectic with the -phase of the NiAs-type. has a congruent melting point of 900.5°C at 56 at% Te and a maximum phase width from 52 at% Te (690°C) to 66.6 at% Te (448.5°C). Te and the -phase form a degenerate eutectic at 448.5°C. The phases 2, 1, and were verified by X-ray diffraction and the lattice parameters of the -phase were determined as a function of concentration.


Mit 2 Abbildungen  相似文献   

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