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1.
Double sulphates of rare earths with dimethylammonium, with empirical formula (CH3)2NH2Ln(SO4)2·4H2O (Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu and Y), were studied by means of thermogravimetry, derivative thermogravimetry and differential thermal analysis from 20 to 700°. Quantitative gravimetric analysis was used for the determination of rare earths and sulphate. The mechanism of thermal decomposition is also suggested.
Zusammenfassung Doppelsulfate der seltenen Erden mit Dimethylammoniumionen der empirischen Formel (CH3)2NH2Ln(SO4)2·4H2O (Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu und Y) wurden mittels TG, DTG und DTA im Temperaturbereich von 20–700° untersucht. Die Seltenen Erden und Sulfat wurden gravimetrisch bestimmt. Ein Mechanismus der thermischen Zersetzung wird vorgeschlagen.

, 20–700° (3)2N2Ln(S4)2·42, Ln=Tb, Dy, , Er, Tm, Yb, Lu Y. . .
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2.
3.
Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.
Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon
Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.
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4.
5.
The use of differential scanning calorimetry has provided enthalpies,H (298 K), of the dissociation reactions RCo(salen) (pyridine) (c) RCo(salen) (c)+pyridine(g)R=Me 34.5, Et 21.9,n-Pr 12.8,i-Pr 11.1,n-Bu 8.3 andi-Bu 13.5 kJ mol–1
Zusammenfassung Mit Hilfe der Differential-Scanning-Kalorimetrie wurden die EnthalpienH(298 K) der Dissoziationsreaktionen RCo(salen)(Pyridin)(c) RCo(saleo)(c)+Pyridin(g) bestimmt: R=Me 34,5, Et 21,9,n-Pr 12,8,i-Pr 11,1,n-Bu 8,3 undi-Bu 13,5 kJ·mol–1.

(298 K) : R() () R ()+() R R = – 34,5; – 21,9; - –12,8; - 11,1; - –8,3 13,5 · –1.
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6.
Analyses of rainwater are routinely performed by a number of organisations to monitor the contribution from rainwater to the component occurrences in the environment and the acidification of the environment. To control the quality of such determinations, the Community Bureau of Reference (BCR) has organised a certification campaign to produce two simulated rainwater reference materials (CRM 408, low mineral content and CRM 409, high mineral content). The materials were carefully prepared (addition of pro analysis and supra pure reagents with the mentioned elements to silica-free deionised water) and its homogeneity and long-term stability were verified. The materials were certified for their contents of ammonium (106 mol/kg) (CRM 409), calcium (7.68 and 15.5 mol/kg), chloride (67.3 and 113 mol/kg), hydronium (16.6 and 48.0 mol/kg), magnesium (6.14 and 12.3 mol/kg), nitrate (20.1 and 78.1 mol/kg), potassium (4.25 mol/kg) (CRM 409), sodium (42.0 and 82.9 mol/kg) and sulphate (10.5 and 53.2 mol/kg). Indicative values (not certified) are given for ammonium and potassium in CRM 408. This paper presents the certification work performed, as well as the analytical work for the certification of the contents of relevant species.  相似文献   

7.
8.
The rare earth-silver-stannides YAgSn, TmAgSn, and LuAgSn were synthesized from the elements by arc-melting and subsequent annealing. The three stannides were investigated by X-ray powder and single-crystal diffraction: NdPtSb type, P63mc, Z=2, a=468.3(1), pm, wR2=0.0343, 353 F2 values, 12 variables for YAgSn, and ZrNiAl type, P6¯2 m, a=726.4(2), , wR2=0.0399, 659 F2 values, 15 variables for TmAgSn, and a=723.8(2), , wR2=0.0674, 364 F2 values, 15 variables for LuAgSn. Besides conventional laboratory X-ray data with monochromatized Mo radiation, the structures were also refined on the basis of synchrotron data with , in order to clarify the silver-tin ordering more precisely. YAgSn has puckered, two-dimensional [AgSn] networks with Ag-Sn distances of 278 pm, while the [AgSn] networks of TmAgSn and LuAgSn are three-dimensional with Ag-Sn distances of 279 and 284 pm for LuAgSn. Susceptibility measurements indicate Pauli paramagnetism for YAgSn and LuAgSn. TmAgSn is a Curie-Weiss paramagnet with an experimental magnetic moment of 7.2 μB/Tm. No magnetic ordering is evident down to 2 K. The local environments of the tin sites in these compounds were characterized by 119Sn Mössbauer spectroscopy and solid-state NMR (in YAgSn and LuAgSn), confirming the tin site multiplicities proposed from the structure solutions and the absence of Sn/Ag site disordering. Mössbauer quadrupolar splittings were found in good agreement with calculated electric field gradients predicted quantum chemically by the WIEN2k code. Furthermore, an excellent correlation was found between experimental 119Sn nuclear magnetic shielding anisotropies (determined via MAS-NMR) and calculated electric field gradients. Electronic structure calculations predict metallic properties with strong Ag-Sn bonds and also significant Ag-Ag bonding in LuAgSn.  相似文献   

9.
Two aqueous methods were followed for the synthesis of MVO4 (M=trivalent element). The first, with vanadium pentoxide and M nitrate yielded crystalline InVO4 III and amorphous FeVO4. The second method, using ammonium metavanadate and M nitrate, led to amorphous compounds with M=In, Fe, Cr or Al, and semi-amorphous compounds with M=Nd or Y. The crystallinity and purity of these products were examined by DTA.Starting with amorphous compounds, two irreversible effects appeared; the first, at about 100°, was endothermic and corresponded to a considerable loss of water; the second was exothermic and corresponded to the crystallization of the compounds in the temperature range from 250 to 550°. Only InVO4 presented two more irreversible exothermic peaks, corresponding to allotropic transformations, as proved by the X-ray diagrams.A reversible effect then appeared, showing an invariant equilibrium corresponding to a peritectic process for InVO4 III, FeVO4, CrVO4 and AlVO4 at 1134, 870 and 765°, respectively; these temperatures agreed with the known M2O3-V2O5 phase diagrams.The DTA curves of the semi-amorphous Nd and Y compounds showed only a loss of water at about 100°; crystallization then occurred gradually during heating; X-ray analysis confirmed these results.
Zusammenfassung MVO4 (M=dreiwertiges Element) wurde nach zwei Methoden in wässrigem Medium dargestellt. Die erste, bei der von Vanadinpentoxid und dem Nitrat von M ausgegangen wird, ergibt kristallines InVO4 III und amorphes FeVO4. Die zweite, von Ammoniummetavanadat und dem Nitrat von M ausgehende Methode ergibt amorphe Produkte für M=In, Fe, Cr oder Al und halbamorphe für M=Nd oder Y. Kristallinität und Reinheit dieser Produkte wurden mittels DTA untersucht. Bei den amorphen Verbindungen treten zwei irreversible Effekte in Erscheinung, nämlich bei etwa 100° ein durch Abgabe einer beträchtlichen Wassermenge bedingter endothermer Effekt und ein exothermer im Temperaturbereich von 250–550°, der der Kristallisation der Verbindungen zuzuschreiben ist. Nur InVO4 zeigt zwei weitere irreversible exotherme Effekte, die auf allotropische Umwandlungen zurückzuführen sind, wie durch röntgendiffraktometrie gezeigt werden konnte. Danach tritt ein reversibler Effekt ein, der ein invariantes Gleichgewicht eines peritektischen Prozesses für InVO4 III, FeVO4, CrVO4 und AlVO4 bei 1134, 870, 880 bzw. 765° anzeigt. Diese Temperaturen stimmen mit den bekannten Phasendiagrammen von M2O3-V2O5 überein. Die DTA-Kurven der halbamorphen Nd- und Y-Verbindung lassen nur den Wasserverlust bei 100° erkennen, die Kristallisation erfolgt dann nach und nach während des Aufheizvorganges, wie dusch Röntgenanalyse gezeigt werden konnte.

MVO4 (M — ) . , , InVO4 FeVO4. , , , , — . . : 100° , , 250–550°, . InVO4 , , , . InVO4, FeVO4, CrVO4 AlVO4 , , 1134, 870, 880 765°, , . , 23-V2O5. - 100°. .


Paper presented at the World Conference on Thermal Analysis Amsterdam, 1984.  相似文献   

10.
A simultaneous TG, DTG, DTA and EGA method was developed for the determination of carbonate, sulphate, pyrite and organic material in minerals. The method is based on the selective direct determination of SO3 and CO2 evolved from the heated sample, and on the indirect determination of H2O. The thermogas-titrimetric adapter of the derivatograph collects the liberated gases (CO2, SO3, SO2) quantitatively, absorbs them in water, and titrates them continuously and automatically with NaOH titrant. The changes in the volume of titrant consumed are recorded as a function of the temperature. In two parallel examinations, one titration is performed at pH 4, and the other at pH 9.3. The former measurement yields only the amount of SO3 (SO2), while the latter gives the joint amount of SO3 (SO2) and CO2.
Zusammenfassung Autoren entwickelten eine Methode zur simultanen TG, DTG, DTA und EGA zur Bestimmung von Karbonaten, Sulfaten Pyrit und organischem Material in Mineralen. Die Methode basiert auf der selektiven direkten Bestimmung des beim Erhitzen der Probe entwickelten SO3 bzw. CO2 und der indirekten Bestimmung von Wasser. Die in Freiheit gesetzten Gase (CO2, SO3, SO2) werden im gastitrimetrischen Adapter des Derivatographen gesammelt, in Wasser absorbiert und kontinuierlich und automatisch mit NaOH titriert. Das Volumen der verbrauchten Titrierflüssigkeit wird in Abhängigkeit von der Temperatur registriert. In zwei Parallelversuchen wird eine Titration bei pH 4, die andere bei pH 9.3 ausgeführt. Die erstere Messung ergibt nur die Menge an SO3 (SO2), während bei der letzteren die Gesamtmenge an SO3 (SO2) und CO2 erhalten wird.

, , ( ) , , . SO3 CO2, , . - (CO2, SO3, SO2), . ë . : pH=4, - pH=9.3. SO3(SO2), — SO3(SO2) CO2.


The authors thank Prof. E. Pungor for valuable discussions, and Mrs. M. Kiss and Miss I. Fábián for their technical assistance.  相似文献   

11.
The possibility of obtaining 2-aryl-substituted benzoxazoles and naphthoxazoles by heating o-nitrophenols, o-nitronaphthols, and -mtroso--naphthol with aromatic aldehydes in highboiling solvents with simultaneous removal of the water formed by distillation is demonstrated.Communication VI of the series Structure and Properties of Nitroso Compounds. See [1] for communication V.The preparation of XVI was carried out in mesitylene, while the other compounds were prepared in tetralin (10–20 ml of solvent per 0.03 mole of the hydroxy compound). In the preparation of III, VIII, XIII, and XVI-XVIII, 3 moles of aldehyde were introduced into the reaction per mole of hydroxy compound, while 5 moles of the aldehyde per mole of hydroxy compound were used in the remaining cases. Compounds XVI-XVIII were obtained from -nitroso--naphthol, XXI-XXIIwere obtained from -nitro--naphthol, and XIX-XX were obtained from -nitro--naphthol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 10–11, January, 1972.  相似文献   

12.
FT-Raman spectra of 2-, 3-, and 4-chlorostyrene included in-cyclodextrin (CD),glycerol ether -CD, -CD,sulfated -CD, andglycerol ether -CD were recorded.In the inclusion complexes, the area of the vinyl(C=C) band decreased remarkably, whereasthe area of the phenyl (C=C) band increasedcompared to those of liquid 2-, 3-, and 4-chlorostyrene,respectively. From the results, the inclusion structures of2-, 3-, and 4-chlorostyrene were discussed.  相似文献   

13.
From the leaves of Algerian ivyHedera canariensis Willd. (fam. Aralaceae) we have isolated 13 triterpene glycosides: the 3-O--L-arabinopyranosides of oleanolic acid (A), of echinocystic acid (B1), and of hederagenin (B2); the 3-O-[O--L-rhamnopyranosyl-(2)--L-arabinopyranoside]s of oleanolic acid (C), of echinocystic acid (D), and of hederagenin (E1); the 3-O--L-rhamnopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside of hederagenin (G1); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O--gentiobioside of hederagenin (G3); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside]s of oleanolic acid (G2), of echinocystic acid (H1), and of hederagenin (H2); the 3-O-[O--L-rhanmopyranosyl-(12)--D-glucopyranoside] 28-O-(O--L-rhamno-pyranosyl-(14)--gentiobioside] of hederagenin (H2); and the 3-O-(O--L-rhamnopyranosyl-(12)-O-gentiobiosyl)-O-(14)--L-rhamnopyranosyl-(12)-a-L-arabinopyranoside] of hederagenin (G4). The structures of the substances isolated have been established on the basis of chemical transformations and13C NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 377–383, May–June, 1996. Original article submitted December 3, 1995.  相似文献   

14.
Circular dichroism (CD) and visible spectra of inclusion compounds between Methyl Orange (MO) analogues and -, -, -cyclodextrin (cdx), 2,6-dimethyl-and 2,3,6-trimethyl--cdx, water soluble -, -, -cdx polymer products were investigated. In the CD-spectroscopic investigation, the complex with -cdx epichlorohydrin condensate showed a large amplitude and splitting of the induced * band. Fractions of glyceryl ether of less than 2000 and polymer of more than 10000 dalton molecular mass were separated. Complexes of above two fractions and MO showed the same splitting spectral pattern. Job's plots from visible spectra showed the formation of the 11 complex and CD-data suggested the co-existence of the 21 MO-cdx complex. This splitting pattern showed the reversal of the signs when -cdx-ethyleneglycol-bis(epoxypropyl) ether was used and disappeared when larger host molecules and azo dyes were used. The splitting was explained by exciton interaction.  相似文献   

15.
Starting from (+) (2R) methyl 5-ethyl-2,2-spirobiindane-5-carboxylate of known enantiomeric purity 79 optically active, configurationally correlated 5,5,6-trisubstituted 2,2-spirobiindanes (2–7) were prepared for the purpose of testing a shortened polynomal Ansatz for chirality functions. Their optical rotations and1H-nmr spectra are reported.In this context several 6-substituted 5-ethylindanes (1) were prepared as model compounds for synthetic transformations.
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16.
On the basis of thermomagnetic and DTA measurements, together with data from the literature, it may be concluded that in some f.c.c. metals a phase transformation occurs just before melting.
Zusammenfassung Auf Grund thermomagnetischer und differentialthermoanalytischer Messungen sowie Literaturangaben wird geschlossen, dass in manchen kubisch-flächenzentrierten Metallen wenig unterhalb der Schmelztemperatur eine reversible Phasenumwandlung, wahrscheinlich in eine kubischraumzentrierte oder amorphe Phase, stattfindet.

, , , .
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17.
Rare-earth orthoferrites, RFeO3, and rare-earth iron garnets (RIGs) R3Fe5O12 (R=rare-earth elements) were prepared by citrate-nitrate gel combustion method and characterized by X-ray diffraction method. Isobaric molar heat capacities of these oxides were determined by using differential scanning calorimetry from 130 to 860 K. Order-disorder transition temperatures were determined from the heat capacity measurements. The Néel temperatures (TN) due to antiferromagentic to paramagnetic transitions in orthoferrites and the Curie temperatures (TC) due to ferrimagnetic to paramagnetic transitions in garnets were determined from the heat capacity data. Both TN and TC systematically decrease with increasing atomic number of R across the series. Lattice, electronic and magnetic contributions to the total heat capacity were calculated. Debye temperatures as a function of absolute temperature were calculated for these compounds. Thermodynamic functions like , , Ho, Go, , , , , and have been generated for the compounds RFeO3(s) and R3Fe5O12(s) based on the experimental data obtained in this study and the available data in the literature.  相似文献   

18.
Summary The use of micro reversed phase columns (Polygosil C18) for the separation of metal DDTC chelates was investigated and applied to drinking water analysis.Three different eluents have been tested [702010 (MeOH H2OCHCl3); 8020 (MeOHH2O); 7030 (MeOHH2O)] at flow rates of 7 to 28gml/min. Eluent composition showed strong influence onk of Co(DDTC)2.The linear working curves fitted at least 3 decades with detection limit of 40–500 pg. Monitoring at max instead of 254 nm decreases the detection limits. The consume of eluent is 10 to 20 times less than with analytical columnes.Results of micro LC have been compared with predictible data of theoretical considerations.
Mikro-Umkehrphasen-Flüssigkeitschromatographie der Cd-, Ni-, Zn-, Cu-, Co-, Hg-Diethyldithiocarbamatchelate im Picogrammbereich
Zusammenfassung Die Anwendung von Mikro-RP-Säulen (Polygosil C18) für die Trennung von Metall-DDTC-Chelaten wurde untersucht und auf die Analyse von Trinkwasser angewendet. Drei verschiedene Eluentien [702010 (MeOH H2OCHCl3); 8020 (MeOHH3O); 7030 (MeOHH2O)] bei Fließraten von 7 bis 28gml/min wurden untersucht,k von Co(DDTC)2 wird von der Eluenszusammensetzung erheblich beeinflußt. Der lineare Meßbereich betrug mindestens 3 Dekaden mit einer Nachweisgrenze von 40–500 pg, die durch Detektion bei max statt bei 254 nm noch weiter gesenkt werden kann.Der Verbrauch an Eluens ist 10–20mal geringer als bei analytischen Säulen.Die Ergebnisse der Mikro-LC wurden anhand theoretischer Überlegungen mit den vorhersagbaren Daten verglichen.


Presented in parts at 9th International Symposium on Microchemical Techniques, Amsterdam 1983.  相似文献   

19.
Solution-gel-crystal phase transitions in a polysaccharide-water-salt system were examined. Polysaccharide helices were shown to exhibit identical conformation in solutions, gels, and crystals containing up to 50 % of water.Translated fromIzvestiya Akademii Nauk. Seriya Khitnicheskaya, No. 6, pp. 1543–1546, June, 1996.  相似文献   

20.
Summary Studies were conducted on the assay of Sm, Eu, Dy and Er separated from uranium using aqueous standards by electrothermal AAS with Massmann type graphite furnace. The working curves were found to be linear in the ranges Sm (1–10 g/ml), Eu (0.05–0.6 g/ml), Dy (0.1–0.8 g/ml) and Er (0.1–1.0 g/ml). The values obtained for synthetic samples agreed favourably with those obtained by emission spectrographic method. Experiments using pyrolytic carbon coated tubes with and without pretreatment by La, Ta and Y have shown an enhancement with treatment upto a maximum of 15% and improve the memory effect marginally. The effect of Ta treatment was found to be singularly useful in improving the general behaviour of Sm. The interference effects of lanthanides, other than the analyte, were found to be negligible. However, the presence of uranium was found to affect the absorbance. The absorbance of Eu was found to be nearly independent of uranium after an initial increase. On the other hand, the absorbance of other elements studied was found to drastically decrease after an initial enhancement. Detailed investigations of temperature dependence of absorbance were carried out using Eu, Dy and Er. The differences in the behaviour of these elements is attributed to probable differences in the modes of their atomization.
Untersuchung von aus Uran abgetrenntem Samarium, Europium, Dysprosium und Erbium durch elektrothermische Atomabsorptions-Spektralphotometrie
Zusammenfassung Die Untersuchungen wurden mit Hilfe des Graphitrohrofens nach Maßmann durchgeführt. In folgenden Bereichen ergaben sich lineare Eichkurven: Sm 1–10 g/ml, Eu 0,05–0,6 g/ml, Dy 0,1–0,8 g/ml, Er 0,1-1,0 g/ml. Die aus synthetischen Proben erhaltenen Ergebnisse stimmten gut mit den durch Emissionsspektrographie erhaltenen überein. Versuche wurden mit Röhren mit pyrolytischen Kohlenstoffüberzug mit und ohne Vorbehandlung durch La, Ta und Y durchgeführt und ergaben eine bis 15%ige Steigerung durch die Behandlung sowie eine mäßige Besserung des Memoryeffektes. Eine Behandlung mit Ta war besonders für Sm vorteilhaft. Störungen durch andere Lanthanide waren vernachlässigbar. Uran beeinflußte jedoch die Absorption. Im Falle von Eu zeigte sich nach anfänglicher Zunahme fast eine Unabhängigkeit, während bei den anderen untersuchten Elementen nach anfänglicher Zunahme eine beträchtliche Abnahme auftrat. Mit Eu, Dy und Er wurde ebenfalls die Temperaturabhängigkeit der Absorption untersucht. Festgestellte Unterschiede im Verhalten werden auf unterschiedliche Atomisierung zurückgeführt.
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