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1.
A conductance study concerning the association of Na+, K+, Rb+, and Cs+ with 1,13-dibenzo-24-crown-8 in acetonitrile has been carried out at 35, 30, 25, 20, and 15°C. The observed molar conductivities were found to decrease significantly for mole ratios less than unity. A model involving 11 stoichiometry has been used to analyze the conductivity data. The stability constant, K, and the molar conductivity C for each 11 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of log K at 25°C, is found to be Rb+>Cs+>K+>Na+. Values of Ho and So are reported and their significance is discussed.  相似文献   

2.
MoO3/Al2O3 is reduced at least partly by sulfur which is formed from H2S in sulfidation with H2S/N2 mixture. SO2 formation during TPD of MoO3/Al2O3 with presorbed H2S provides evidence for the explanation.
MoO3/Al2O3 , H2S/N2. SO2 MoO3/Al2O3, H2S, .
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3.
Fe/Mn/K catalysts derived from support of the anionic carbonyl, [Fe2Mn(CO)12] on silica were compared with catalysts prepared by aqueous impregnation methods, and found to be more selective for production of C2–C4 olefins. Addition of K had little effect, whereas variations in reaction conditions altered selectivity owing to secondary reactions of the alkene products.
Fe/Mn/K, , [Fe2Mn(CO)12], , , , C2–C4. , , .
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4.
A criterion for the selection of a suitable plasticizer for calix[n]arene-based ion-selective electrodes is discussed. The cation selectivity of plasticized membranes without the ligand was first measured as a reference. The membranes can be roughly classified into two groups. The first group shows cation selectivity in the order Cs++>K+>Na+>Li+. The membranes in the second group are made of phosphorus plasticizers, which show a selectivity in the reverse order. The plasticizers in the first group featured a linear relationship between the dipole moment of the plasticizer (calculated by a PM3 method) and the ratio of cesium selectivity to lithium selectivity. The linear relationship supports the view that the polar membrane which includes a soft plasticizer with a large dipole moment shows selectivity for Cs+, whereas the nonpolar membrane including the soft plasticizer with the small dipole moment shows much lower selectivity for Cs+. Next, 2-fluorphenyl-2-nitrophenyl ether (FPNPE) which showed the highest Cs+ selectivity and tris(2-ethylhexyl)phosphate (TEHP) which showed the highest Li+ selectivity were mixed in an appropriate ratio to make membranes with a different affinity for hard ions. The metal selectivities of several crown-based and calixarene-based ionophores were examined in these membranes. Although a few exceptions exist, the polar soft membrane is favorable when the interfering metal ion is hard, whereas the hard membrane is favorable when the interfering metal ion is soft.  相似文献   

5.
Summary The interaction of copper(II) salts with the imidazole-containing disulphide 5-(1,2,5-dithiazaepan-5-ylmethylene)-4-methyl-2-ethyl imidazole (MAMI) in MeOH have been investigated. The 11 Cu(ClO4)2MAMI system exhibited a single ligand field band at ca. 12200cm-1, an intense shoulder at ca. 31500 cm-1 and a less intense split feature at 24400 and 25300cm-1 assignable to S() CuII and S() CuII charge transfer (CT) transitions, respectively. The e.p.r. parameters suggested the presence of a CuN2SO chromophore, however; the 11 Cu(NO3)2MAMI system did not exhibit a S CuII CT band and the g value was comparatively high. An electrochemical study of the 11 Cu(ClO4)2MAMI system in MeOH revealed that the copper-disulphide interaction, though weaker, would confer a high redox potential as well as reversibility, similar to the copper-thioether interaction.  相似文献   

6.
TheSomogyi-Nelson colorimetric method is applied in a new manner more suitable for evaluating the kinetics of the enzyme hydrolysis of sodium carboxymethylcellulose (Na-CMC) catalyzed by the cellulase complex. By means of selective inhibition of a chosen enzyme from the cellulase complex it became possible to trace the effect of the other enzymes included in its composition.
Kinetik und Mechanismus der Hydrolyse von Natriumcarboxymethylcellulose (Na-CMC) durch einen Cellulase-Komplex
Zusammenfassung Die kolorimetrische Methode nachSomogyi undNelson wird nach einem neuen Verfahren zur Verfolgung der Kinetik der hydrolytischen Spaltung von Natriumcarboxymethylcellulose (Na-CMC), katalysiert durch den Cellulase-Komplex, angewandt. Durch selektive Inhibierung eines bestimmten Enzyms des Cellulase-Komplexes kann man die Wirkung der anderen zu seiner gesamten Zusammensetzung gehörenden Enzyme verfolgen.

Symbols Used E enzyme (E—cellulase;E—exo-cellobiohydrolase;E—-glucosidase) - [E] w weight concentration of enzymeE - S substrate (Na-CMC—sodium carboxymethylcellulose) - [S]0 weight concentration of substrateS - I inhibitor (I—lactose;I—calcium chloride;I—condurrite-B-epoxide) - P product (P—oligosaccharides;P—cellobiose;P—D-glucose) - P end product (K , K , K ) - DP degree of polymerization - DS degree of substitution - ES enzyme-substrate complex (E S, E S, E S) - EP enzyme-product complex (E P, E P) - EI enzyme-inhibitor complex (E I, E I, E I) - M s molecular mass of substrateS - K s substrate constant (K s , K s , K s ) - K I inhibitor constant (K I , K I , K I ) - K m Michaelis-Menten constant - k +1,k +2 (k +2 ,k +2 ,k +2 ) forward rate constants - k –1 reverse rate constant - 0 initial rate of reaction - V maximal reaction rate - A change in absorbance - molar absorption coefficient - wavelength Herrn Prof. Dr.Hans Tuppy zum 60. Geburtstag herzlichst gewidmet.  相似文献   

7.
Zusammenfassung Es wurde die thermische Analyse des Caesiumjodobismuthats(III) ausgeführt. Aus den Ergebnissen dieser sowie der chemischen und diffraktometrischen Analysen der Sinterprodukte wurde der Reaktionsmechanismus der thermischen Zersetzung dieser Verbindung festgestellt.
The thermal analysis of caesiumjodobismuthate(III) was carried out. From the results and the chemical and diffractometric analysis of sinters, the mechanism of thermal decomposition of this compound was established.

(III) . , .
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8.
The complexation thermodynamics of polymethylene andm-phenylene bridged carbonylhydrazones of 4-formylbenzo-15-crown-5 with K+, Rb+, Cs+ and Tl+ was investigated by spectrophotometric titrations in methanol at 283–313 K. The carbonylhydrazone sequences in the bridge of the bis(benzocrown ether)s are optical sensors for the sandwich complexation of metal ions. Within the homologous series of polymethylene bridged carbonylhydrazones a stability peak was found for the sandwich complexes of the propylene bridged compound with K+, Rb+ and Tl+. The potassium complex of this ligand shows the highest stability constant compared to all other known bis(benzo-15-crown-5) complexes with K+ in methanol.In terms of thermodynamics the formation of intramolecular sandwich complexes is driven by a gain of enthalpy. The unusual high gains of enthalpy and losses of entropy on formation of the most stable sandwich complexes allow us to propose an additional stabilization of the sandwich arrangement by intramolecular hydrogen bridge bonds. The H o-TS o diagram gave an excellent straight line allowing discussion of the enthalpy-entropy compensation effect at these complexation reactions.  相似文献   

9.
The kinetics of oxidation of thiocyanate ion by Bromamine-T (BAT) has been investigated in alkaline medium. The rate of reaction is first order in [OH] and zero order in [NCS]. The pseudo-first order rate constants decrease with increase in [BAT]. Addition of the reaction products p-toluenesulfonamide, Br and neutral salts has no significant effect on the rate. The rate increases with either increase in ionic strength or decrease in dielectric constant of the medium. The activation parameters have been computed. A mechanism consistent with the experimental results has been proposed and the rate law derived. The rate constants predicted from the rate law for the variation of [BAT] are in excellent agreement with the observed rate constants.
- (BAT) . [OH] [NCS]. [BAT]. -, Br . . . , , . , , [BAT]o, .
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10.
The frequency response of a diffusion transducer with gauze electrodes, studied theoretically at high frequencies, is proportional to -3/2 starting with = D/R 2 at < /R 2 and to -1 at > /R 2. Here, = 2f, f is the signal frequency, the electrolyte viscosity, D a diffusion coefficient, and R the radius of the gauze filaments. The calculation is compared with experiment.  相似文献   

11.
The oxygen nonstoichiometry (x) of LaTa2-2xNb2xVO9- (x = 0–0.1) solid solutions was studied using Xray phase analysis, vibrational spectroscopy, and radiospectroscopy. A correlation was found between (x) and the unit cell volume V(x) of the solid solutions. It was shown that the infrared spectra of LaTa2VO9- change in passing from = 0 to 0. The structural position of the oxygen vacancy in LaTa2-2xNb2xVO9- is discussed.  相似文献   

12.
MP2/6-31+G* calculations were performed on the cation- complexes of ethylene, cyclobutadiene and benzene with a number of atomic cations. It was found that except B+ all the atomic cations form -type cation- complexes with ethylene. On the other hand, with cyclobutadiene Li+, N+, Na+, P+ and K+ form -type complexes, whereas H+, F+, and Cl+ form covalent -type complexes. With benzene Li+, B+, Na+, Al+, and K+ form -type complexes whereas H+, F+, and Cl+ form -type complexes. It was concluded that the driving force to form the -type complex is chemical bonding, and that for metal cations to form -type complexes is non-covalent interaction.  相似文献   

13.
Conclusions Members of a new class of-hydroxy--amino acids of the pregnane series were synthesized by the reductive cleavage of steroido[16,17-d]isoxazolines.See [1] for Communication 109.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1139–1141, May, 1980.  相似文献   

14.
Piloyan activation energiesE as well as initals of exothermT D of sevenN-monoalkyl and fiveN,N-dialkyl-2,4-dinitroanilines were determined. Relationships were found between the TD values and Rf factors as well asE values and those RM functions and also theET D –1 term and RM functions.
Zusammenfassung Die AktivierungsenergienE nach Piloyan sowie die Anfangswerte der ExothermenT D wurden für siebenN-Monoalkyl- und fünfN,N-Dialkyl-2,4-dinitroaniline bestimmt. Die Zusammenhänge zwischen denT D-Werten und den papierchromatographischenR f-Faktoren der gemessenen Dinitroaniline wurden abgeleitet und erörtert. Desgleichen wurden auch die Zusammenhänge zwischen denE-Werten und denR M-Funktionen der Papierchromatographie abgeleitet und erörtert. Auch zwischen dem AusdruckE ·T D –1 und denR M-Funktionen wurde ein Zusammenhang gefunden.

Résumé On a déterminé les températures initialesT D de l'effet exothermique ainsi que les énergies d'activationE d'après la méthode de Piloyan, de sept N-mono alcoyl et cinqN,N-dialcoyl-2, 4-dinitroanilines. Une corrélation entre les valeursT D et les facteursR f de la Chromatographie sur papier des dinitroanilines étudiées a été trouvée et discutée, ainsi qu'entre les valeursE et les fonctionsR M de la Chromatographie sur papier. Une relation entre le termeE ·T D –1 et les fonctionsR M a également été trouvée.

E T D N- N,N- -2,4- . D R f , E R M. E. D –1 R M.


The authors would like to thank Mrs. Anna Collàkovà for careful DTA measurements, and Dr. Ladislav Smolka for help in treatment of the measured results with the Wang 600 computer.  相似文献   

15.
The apparent equivalent volume V, expansibility E, and compressibility K of an artificial seawater solution containing10 ionic components (Na+, Mg2+, Ca2+, K+, Sr2+, Cl, SO 4 2– , HCO 3 , Br, and F) and one nonionic component (H3BO3) has been determined from0 to40°C (in5° intervals) and from0.1 to0.8 m ionic strength at1 atm. The concentration dependence (Iv=volume ionic strength) of the V's, E's, and K's have been examined by using a Masson-type equation, = ° +S'I V 1/2, and a Redlich-type equation, = ° +SI V 1/2 +BI V, where ° is the infinite-dilution value, S is the empirical Masson slope, S is the theoretical Debye-Hückel slope, and B is an empirical deviation constant. By using Young's rule, = Ei(i), the apparent equivalent volumes, expansibilities, and compressibilities for sea salt have been estimated from the ionic and nonionic components making up the mixture. The estimated apparent molal quantities agree very well with the directly measured values providing the concentration terms, S i and Bi, are weighted according to the methods of Wood and Reilly.Contribution Number 1599 from the University of Miami.  相似文献   

16.
The pseudobinary systems ACl/CeCl3 (A=Na-Cs) were reinvestigated by means of DTA. The following compounds were found and identified through their X-ray patterns (primarily detected compounds in italics):NaCe 1.67 Cl 6; K3CeCl6, K2CeCl5,KCe 1.67 Cl 6;Rb 3 CeCl 6, Rb2CeCl5,RbCe 2 Cl 7; Cs3CeCl6, Cs2CeCl5,CsCe 2 Cl 7. The compounds A2CeCl5 crystallize with the K2PrCl5 structure. The high-temperature modifications of the compounds A3CeCl6 have the cubic elpasolite structure. The hexagonal unit cell of KCe1.67Cl6 is related to the CeCl3 structure: 0.33 Ce3+ are substituted by one Ks+. The structure of CsCe2Cl7 can be described with a hexagonal subcellZ=4,a=9.72 andc=14.94 Å; however, small superstructure reflexions reduce the symmetry.The thermodynamic functions for the reactionsnACl+CeCl3=A n CeCl n+3(A=K, Rb) were determined by means of e.m.f. measurements.Measurements of the e.m.f.E vs. T yielded the Gibbs enthalpiesG r . The temperature-dependence was found to be linear.The most important result is the formation of the elpasolites (A3CeCl6) and ACe2Cl7.
Zusammenfassung Die pseudobinären Systeme ACl/CeCl3 (A=Na-Cs) wurden mittels Differenzthermoanalyse (DTA) neu untersucht. Folgende Verbindungen wurden gefunden und durch ihre Röntgenbeugungsmuster charakterisiert (erstmalig nachgewiesene Verbindungen sind kursiv):NaCe 1.67 Cl 6; K3CeCl6, K2CeCl5,KCe 1.67 Cl 6;Rb 3 CeCl 6, Rb2CeCl5,RbCe 2 Cl 7; Cs3CeCl6, Cs2CeCl5,CsCe 2 Cl 7. Die Verbindungen A2CeCl5 kristallisieren im K2PrCl5-Typ. Die Hochtemperaturmodifikationen der Verbindungen A3CeCl6 liegen in der kubischen Elpasolith-Struktur vor. Die hexagonale Elementarzelle des KCe1.67Cl6 ist mit der CeCl3-Struktur verwandt: 0,33 Ce3+ sind durch ein K+ ersetzt. Die Struktur des CsCe2Cl7 kann mit einer hexagonalen Pseudozelle beschrieben werden:a=9,72;c=14,94Å;Z=4; schwache Überstrukturreflexe reduzieren jedoch die Symmetrie. Die thermodynamischen Funktionen für die Reaktionen:n ACl + CeCl3=A n CeCl n+3 (A=K, Rb) wurden durch EMK-Messungen bestimmt. Messungen der Abhängigkeit von e. m. f.E gegenT ergaben die Gibbs-EnthalpienG r . Es wurde eine lineare Temperaturabhängigkeit gefunden. Als wichtigstes Resultat ist die Bildung von Elpasoliten (A3CeCl6) und von Verbindungen (ACe2Cl7) anzusehen.

ACl/CeCl3, A . - ( ):NaCe 1.67 Cl 6; K3CeCl6, K2CeCl5,KCe 1.67 Cl 6;Rb 3 CeCl 6, Rb2CeCl5,RbCe 2 Cl 7; Cs3CeCl6, Cs2CeCl5 CsCe 2Cl7. A2CeCl5 K2PrCl5. A3CeCl6 . KCe1.67Cl6 CeCl3, 0,33 Ce3+ . CsCe2Cl7 a=9,72 Å,c=14,94 Å Z=4. , . n ACl + CeCl3=A n CeCl n+3(A=K, Rb) . . . . . .E , G r . ACe2Cl7.


Presented as a poster at the 8th ICTA, Bratislava, 1985.

This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.  相似文献   

17.
The Piloyan activation energiesE, as well as the initial exotherm temperaturesT D, are determined for sixN-monoalkyl- and fiveN,N-dialkyl-2,4,6-trinitroanilines. By comparison withR f-factors, orR M-functions of paper chromatography, the molecular-structural dependences ofE andT D are studied for these compounds. Relationships are also found between the termE · T D –1 and theR M-functions. The effects are discussed of the introduction of the 6-nitro group into the TV-substituted 2,4-dinitroanilines, and of the introduction of the 4-nitro group into the 2,6-dinitro analogues, upon the thermal stabilities of the resulting 2,4,6-trinitroanilines.
Zusammenfassung Die AktivierungsenergienE nach Piloyan und die Anfangswerte der ExothermenT D der sechsN-monoalkyl- und fünfN,N-Dialkyl-2,4,6-trinitroaniline wurden bestimmt. Unter Berücksichtigung des Vergleichs mitR f-Faktoren oderR M-Funktionen der Papierchromatographie wurden die molekularstrukturellen AbhÄngigkeiten der WerteE undT D dieser Verbindungen untersucht. ZusammenhÄnge wurden auch zwischen dem AusdruckE · Tw D –1 und denR M-Funktionen gefunden. Der Einfluss der Einführung der 6-Nitrogruppe in dieN-substituierten 2,4-Dinitroaniline, sowie der Einfluss der Einführung der 4-Nitrogruppe in 2,6-Nitroanaloge auf die ThermostabilitÄt der resultierenden 2,4,6-Trinitroaniline werden erörtert.

Résumé On a déterminé les énergies d'activation par la méthode de Piloyan ainsi que les températures initialesT D de l'effet exothermique de sixN-monoalcoyl- et cinqN,N-dialcoyl-2,4,6-trinitroanilines. En se référant aux facteursR F ou aux valeurs des fonctionsR M en Chromatographie sur papier, on a étudié la dépendance entre les valeurs deE et deT D sur les caractéristiques moléculaires-structurales de ces composés.On a également trouvé des rapports entre le termeE · T D –1 et les fonctionsR M. On discute l'influence de l'introduction du groupe 6-nitro dans les 2,4-dinitroanilinesN-substituées ainsi que l'influence de l'introduction du groupe 4-nitro dans les 2,6-dinitro analogues sur la stabilité thermique des 2,4,6-trinitroanilines qui en résultent.

N-- N,N--2,4,6- E , T D. R f,- R M — , - E T D. E.T D –1 R M-. 6N- 2,4- 4 2,6- 2,4,6- .


The authors would like to thank Mrs. Anna Colláková for careful DTA measurements, and Dr. Ladislav Smolka for help in the treatment of the measured results with the Wang 600 computer.  相似文献   

18.
Thermal studies have been carried out on [NiL3]X2·n H2O, whereL=1,2-propanediamine;X=Cl, Br, SCN, 1/2SO 4 2– and 1/2 SeO 4 2– ; andn= 2, 1.5 and 0. [Ni2L5(NCS)2](SCN)2 and [NiL2SO4] have been synthesized pyrolytically in the solid-state from their mother diamine complexes. The deaquation behaviour of [NiL3]SO4·2 H2O appears interesting, and its monohydrate undergoes a solid-state reaction (88–102°) without mass loss, showing an exothermic peak at 95 °C (H=– 5.1 kJ mole–1).
Zusammenfassung Thermische Untersuchungen wurden an [NiL3]X2,n H2O ausgeführt, wobeiL-1,2-Propandiamin;X=Cl, Br, SCN, 1/2 SO 4 2– und 1/2 SeO 4 2– ;n=2, 1.5 und 0. [Ni2Ls(NCS)2](SCN)2 und [NiL2SO4] wurden ausgehend von den entsprechenden Diaminkomplexen pyrolytisch im festen Zustand synthetisiert. Das Dehydratisierungsverhalten von [NiL3]SO4·2 H2O scheint interessant zu sein, und beim entsprechenden Monohydrat wird eine ohne Massenverlust verlaufende Festkörperreaktion (88–102°) beobachtet, die sich durch einen exothermen Peak bei 95 °C (H=– 5.1 kJ mol–1) zu erkennen gibt.

[N3L3]2· n2O, L=1,2-,=l, Br, SCN, 1/2 SO 4 2- , 1/2SeO 4 2- , an=2, 1.5 0. [Ni2L5(NCS)2](SCN)2 [NiL2SO4] . [N3L3]S4·2 2 , 88–102° , 95 ° =– 5.1 ·–1.
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19.
The limiting molar conductances ° of deuterium chloride DCl in D2O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances °E(D +), as estimated by the equation [°E(D +) = °(DCl/D 2 O) – °(KCl/D 2 O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°E(H +) = °(HCl/H 2 O) – °(KCl/H 2 O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °E(H +)/°E(D +) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D2O and H2O.  相似文献   

20.
Bioaccumulation of six metals (Cu2+, Cu+, Mo6+, Mn2+, V5+, Ni2+) and their combinations by algaScenedesmus quadricauda was determined by using radio nuclide X-ray fluorescence (RXFA). The metals were added into the cultivation medium in concentrations corresponding with EC50 value for each metal. The obtained results indicate that Ni2+, Cu2+ and Cu+ were accumulated in high amounts (20%, 17.5% and 15.19%) the Mo6+ ion (<0.2%) was accumulated in the lowest amount. For metal-metal interactions in accumulation of metal ions by algaS. quadricauda three types of answers were determined: inhibition (MoCu2+, Ni, Mn, V; VNi, Mn; MnNi, Cu2+, Cu+; Cu+Ni; Cu2+Ni; NiMn, V), enhancement (VCu+; Cu2+Mn;Cu+V, Mn; MnV; NiCu2+, Cu+) and neutral effect (VMo; Cu2+Mo; Cu+Mo; MuMo; NiMo).  相似文献   

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