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1.
The -radiolysis of Methyl Red solution in HCl medium at pH=2 has been studied along with energy transfer reaction brought about byF and hole centers of -irradiated NaCl. The G-values for degradation of the azo dye indicator by radiolysis and -irradiated salt were determined as 9·10–1 and 4.8·10–3, respectively. The kinetic rate constants (k) of degradation are evaluated as 2·10–5 rad–1 in the case of direct radiolysis, while for the irradiated salt it is 2·10–7 rad–1. The extent of degradation by direct -radiolysis is 100–200 times greater as compared to that by the -irradiated salt. The same mechanism is proposed for radiolysis as well as the reaction induced by -irradiated sodium chloride.  相似文献   

2.
Equilibrium of complexation between 2-hydroxypropylene-1,3-diamine-N,N,N,N-tetraethanoic acid (H4L) and u2+ ions was studied by potentiometric and spectrophotometric methods. Stability constants of CuL2– and CuHL complexes were determined at 298.15 K and I = 0.5 (KNO3).  相似文献   

3.
On the basis of the Berlin diagram, the region-functional contribution of the electron density has been quantitatively examined for the Is, 2p, and 2p states of HeH2+ system. The binding and antibinding contributions and the dynamic behaviours of the electron density during the interaction processes are discussed in comparison with the previous results for homonuclear H 2 + system. The effect of coordinate-dependence of the Berlin diagram on the regional partitioning has also been studied.  相似文献   

4.
The heat capacity of high-purity indium has been determined by adiabatic-shield calorimetry in the range 300 to 1000 K. Values of thermodynamic functions have been calculated andC p (1000 K), [H° (1000 K)– (298.15 K)], and [S° (1000 K)–S° (298.15 K)] are (27.11±0.15) J K–1 mole–1, (22873±70) J mole–1, and (41.567 ±0.125) J K–1 mole–1, respectively. The enthalpy of fusion is (3283±7) J mole–1 and the melting temperature (429.77±0.01) K. The premelting heat capacity is compatible with the presence of a mole fractionx 1·10–6 of a liquid-soluble/solidinsoluble impurity in the sample.
Zusammenfassung Die Wärmekapazität von hochreinem Indium wurde im Bereich von 300 bis 1000 K durch adiabatische Schildkalorimetrie bestimmt. Die Berechnungen der thermodynamischen Funktionen:C p (1000 K), [H° (1000 K)–H° (298.15 K)] und [S° (1000 K–S° (298.15 K)] ergab 27.11±0.15 J K–1 Mol–1, (22 875±70) J Mol–1, bzw. (41.567±0.125) J K–1 Mol–1. Die Schmelzenthalpie beträgt (3283±7) J Mol–1 und die Schmelztemperatur (429.77±0.01) K. Die Vorschmelz-Wärmekapazität ist mit der Gegenwart einer Molfraktionx1×10–6 einer flüssig-löslich/fest-unlöslichen Verunreinigung in der Probe vereinbar.

Résumé La chaleur spécifique de l'indium de haute pureté a été déterminée entre 300 et 1000 K par calorimétrie adiabatique. Les valeurs des fonctions thermodynamiques suivantes ont été calculées:C p (1000 K)=(27.11±0.15) J K–1mol–1, [H° (1000 K)–H° (298.15 K)]= (22 875±70) J mol–1 et [S° (1000 K)–S° (298.15 K)]=(41.567±0.125) J K–1 mol–1. L'enthalpie de fusion est (3283±7) J mol–1 et la température de fusion (429.77±0.01) K. La chaleur spécifique de pré-fusion est compatible avec la présence d'une fraction molairex1×10–6 d'une impureté dans l'échantillon, soluble dans le liquide, insoluble dans le solide.

C - 300 1000 . : p(1000 ), [ (1000 ) — H (298,15 )] [S (1000 ) — S (298.15 )], : 27.11±0.15 . –1. –1, 2 2875±70 . –1 41.567±0.125 . – 1–1. 3283±7 .–1, – 429.77±0,01 . - / 1.10–6.


The assistance of Bjørn Lyng Nielsen with the experimental work is recognized with thanks.  相似文献   

5.
Using the Hartree-Fock method the wave functions of Li+, Be2+, O2–, F, Na+, Mg2+, Al3+, S2–, Cl, K+, Ca2+, Sc3+ and Ti4+ have been calculated for the free ion and the ion in a potential well. The main result of these calculations is a contraction of the anion and an expansion of the cation due to the external potential. A comparison of the calculations with an experimental determination of the electron density distribution in NaCl and MgO shows qualitative agreement. The diamagnetic susceptibility , the dipole polarizability d, and the Sternheimer antishielding factor of the ions given above were also calculated for the free ions and the spherical potential ions (SPI). The charged hollow sphere model improves the theoretical values towards the properties determined by experiment.
Zusammenfassung Unter Verwendung der Hartree-Fock-Methode wurden analytische Wellenfunktionen für die Ionen Li+, Be2+, O2–, F, Na+, Mg2+, Al3+, S2–, Cl, K+, Ca2+, Sc3+ und Ti4+ berechnet. Es wurden sowohl die freien Ionen als auch Ionen im Potentialtopf untersucht. Es zeigt sich eine durch das äußere Potential hervorgerufene Kontraktion der Anionen und eine Expansion der Kationen. Der Vergleich der Rechnungen mit experimentellen Bestimmungen der Elektronendichteverteilung in NaCl und MgO zeigt qualitative Übereinstimmung zwischen Theorie und Experiment. Ferner wurden die diamagnetische Suszeptibilität , die Dipolpolarisierbarkeit d und der Antishieldingfaktor (Sternheimerfaktor) sowohl für die freien als auch für die durch ein kugelsymmetrisches Potential gestörten Ionen berechnet. Das hier benutzte Festkörpermodell der geladenen Hohlkugel ergibt Werte, die in guter Übereinstimmung mit dem Experiment sind.

Résumé Les fonctions d'onde de Li+, Be2+, O2–, F, Na+, Mg2+, Al3+, S2–, Cl, K+, Ca2+, Sc3+ et Ti4+ ont été calculées par la méthode de Hartree-Fock pour l'ion libre et pour l'ion dans un puit de potentiel. Le résultat essentiel de ces calculs montre une contraction de l'anion et une expansion du cation sous l'effet du potentiel extérieur. Les densités électroniques calculées et celles obtenues expérimentalement dans NaCl et MgO sont en accord qualitatif. La susceptibilité diamagnétique , la polarisabilité dipolaire d, et le facteur anti-écran de Sterneimer des ions ci-dessus ont été calculés pour les ions libres et pour les ions à «potentiel sphérique» (SPI). Le modèle de la sphère creuse chargée améliore les valeurs théoriques par rapport aux données expérimentales.


D 17 (E. Paschalis, 1967).  相似文献   

6.
The mechanisms of SO2 oxidation catalyzed by iron ions in the droplet phase of the convective cloud in the lower atmosphere were examined. The relations of the catalytic SO2 decrease to the concentration of the iron ions and to the intensity of fluxes to the droplet of the OH (g) and HO 2(g) radicals were characterized. The determining role of the replacement of the low-reactive HO 2(g)(O 2(aq)) radical by the reactive SO 5(aq) radical in the sulfite medium during daytime was revealed. This process occurred due to the coupling of the decay of the radicals and their regeneration in the liquid-phase reactions O 2(aq) + FeOH2+ (aq) Fe2+ (aq) + OH (aq) + O2(aq), HSO 5(aq) + Fe2+ (aq) FeOH2+ (aq) + SO 4(aq)HSO 3 - (aq),O2 (aq) SO 5(aq).  相似文献   

7.
The anharmonic contribution to the heat capacity of any chalcopyrite semiconductor AIBIIIC 2 VI or AIIBIVC 2 V is evaluated. It is shown that the degree of lattice anharmonicity decreases with increasing atomic weight of the constituent atoms of the compounds, and there is no essential difference in the degree of lattice anharmonicity of the two groups of compounds. Except for CdGeAs2, the trend in the Grüneisen constants is the same.
Zusammenfassung Der anharmonische Beitrag zur Wärmekapazität verschiedener Halbleiterverbindungen AIBIIIC 2 VI und AIIBIVC 2 V vom Chalkopyrit-Typ wird bestimmt. Es wird gezeigt, dass die Gitteranharmonizität mit steigender relativer Atommasse der Bestandteile der Verbindungen abnimmt und dass keine wesentlichen Unterschiede in der Gitteranharmonizität beider Gruppen von Verbindungen bestehen. Der Trend der Grüneisen-Konstanten ist der gleiche, ausgenommen bei CdGeAs2.

IIII 2 VI IIIV 2 V . , , , . , CdGeAs2.
  相似文献   

8.
The crystal structure of (3,5-diamino-6-chloro-pyrazine-2-carbonyl)-guanidine picrate has been determined with the use of X-ray diffraction method. The crystals are triclinic, space group PI with a = 10.2980(4) Å, b = 12.4322(4) Å, c = 14.4310(5) Å, = 66.317(2), = 70.077(2), = 72.462(2), Z = 2. The asymmetric unit consists of one amiloride cation, picrate anion, and three DMSO molecules from the solvent, two of which are disordered. The molecules of amiloride and picrate are almost planar. The guanidine group of amiloride is protonated and makes a kind of a salt bridge with phenolate and forms hydrogen bonds with ortho-nitro oxygen atoms of picrate. The pairs of amiloride cation–picrate anion, transformed by the inversion center and translated by 2 a and c, are mutually parallel and are connected by molecules of DMSO. The conformation of amiloride picrate is compared with those in other crystal structures.  相似文献   

9.
Zusammenfassung Für die Elemente Neon, Natrium, Magnesium, Aluminium und Silizium werden mit einem quantenmechanischen Variationsverfahren unter Verwendung einer minimalen STF-Funktionenbasis Röntgenübergänge vom Typ K 1L1L2 berechnet und den K -Satellit-Linien , , 3, 3 and 4 zugeordnet.
Relation between K -Satellits and X-ray-transitions of the type K 1 L 1L 2 for Ne, Na, Mg, Al and Si
STF-Calculations are reported for X-ray-transitions of the type K 1L1L2 for Ne, Na, Mg, Al and Si. It is shown that these transitions are correlated with the K -satellits , , 3, 3 and 4.


Die Wellenfunktionen können auf Anfrage zur Verfügung gestellt werden.  相似文献   

10.
The isothermal compressibilities T for cyclohexane+toluene mixtures at 25, 35, 45 and 60°C have been determined by direct piezometric measurement. By combining our results with supplementary literature data, we have calculated the isentropic compressibility S. Values of the excess functions (VE/p)T, T E and S E were also calculated at four temperatures and their behavior as a function of mole fraction and temperature was studied.  相似文献   

11.
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   

12.
Summary The complexescis--[Co(trien)(ImH)Cl]2+ (ImH=imidazole, trien=1,8-diamino-3,6-diazaoctane),cis--[Co(trien)(Bun-NH2)Cl]2+,cis--[Co(trien)(NH2CH2-CH(OMe)2)Cl]2+ andcis-2-[Co(trien)(py)Cl]2+ (py=pyridine) have been characterised and their kinetics of base hydrolysis studied. Thecis--isomers which have afac-fac arrangement of the trien ligand have values of k OH 25 in the 73 to 253 dm3 mol–1 s–1 range at I=0.1 mol dm–3. Extremely rapid base hydrolysis is observed withcis-2-[Co(trien)(py)Cl]2+ where k OH 25 is 6.65×106 mol3 mol–1 s–1 at I=0.1 mol dm–3. This complex has amer-fac arrangement of the trien ligand with flatsec-NH donor leading to rapid base hydrolysis due to good -overlap between the conjugate base and cobalt(III). The pyridine ligand causes aca. 30 fold rate increase compared with the hydrolysis ofcis-2-[Co(trien)(NH3)Cl]2+.  相似文献   

13.
The kinetics and mechanism of the thermal decomposition of pyrite were examined by the method of quasi-isothermal and quasi-isobaric thermogravimetry (Q-TG). It emerged that by means of this technique the overlapping partial processes of the complicated oxidation and decomposition reactions of pyrite can be separated and studied independently from one another. It was found that the partial reactions FeS2=FeS +S and Fe2O3–x(SO4)x=Fe2O3+SO3 are endothermic processes taking place quasiisothermally and leading to equilibrium, while the oxidation FeS+O2=Fe2O3–x(SO4)x is an exothermic process which takes place in an oscillating manner in a rather broad temperature interval.
Zusammenfassung Autoren untersuchten die Kinetik und den Mechanismus der thermischen Zersetzung von Pyrit durch quasi-isotherme und quasi-isobare Thermogravimetrie (Q-TG). Es stellte sich heraus, daß sich überlagernde Teilprozesse der komplizierten Oxydations- und Zersetzungsprozesse von Pyrit mit Hilfe dieser Technik absondern und unabhängig voneinander untersuchen lassen. Es wurde festgestellt, daß die Teilreaktionen FeS2=FeS+S und Fe2O3–x(SO4)x=Fe2O3+SO3 endotherme Prozesse sind, die quasi-isotherm verlaufen und zu einem Gleichgewicht führen, während die Oxydation FeS+O2=Fe2O3–x(SO4)x ein exothermer Prozeß ist, der oszillierend in einem ziemlich breiten Temperaturintervall verläuft.

(Q-) . . , FeS2=FeS+S Fe2O3–x(S2O4)x=Fe2O3+SO3 , . FeS+O2 =Fe2O3–x(SO4)x , .


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

14.
The conditions for the synthesis of two polymorphous forms of antimony(III) oxofluoride Sb3O2F5 from aqueous solutions are established. The crystal structure of a new polymorphous modification -Sb3O2F5 is determined (monoclinic crystals with a = 6.9548(6) Å, b = 9.1043(7) Å, c = 20.336(2) Å, = 94.167(2)°, V = 1284.2(2) Å3, Z = 8, (calcd) = 5.092 g/cm3, F(000) = 1712, space group P21/n) and the structure of -Sb3O2F5 is refined. The geometric characteristics of crystal structures of antimony(III) oxofluorides SbOF (L- and -forms) are compared with those of Sb3O2F5 (- and -forms).  相似文献   

15.
Parts of the ternary system Ag-P-S were investigated by DTA- and X-ray measurements. The quasibinary section of Ag2S-P4 S10 is described. The thermal behaviour and X-ray diffraction patterns of Ag7PS6, Ag3PS4, Ag7P3S11, Ag4P2S7 and Ag2P2S6 were studied. DTA-diagrams and X-ray powder data are given.
Zusammenfassung Mittels DIA- und Röntgendiffraktionsmessungen wurden Teile des Dreikomponentensystemes Ag-p-s untersucht. Es wird der quasibinäre Schnitt von Ag2S-P4 S10 beschrieben. Weiterhin wurden das thermische Verhalten und die Röntgenbeugungsbilder von Ag7PS6, Ag3PS4, Ag7P3S11, Ag4P2S7 und Ag2P2S6 untersucht. DTA-Diagramme und Röntgen-Pulverdaten werden gegeben.

Ag-P-S. Ag2S-P4SIO. $ Ag7PS6, Ag3Ps4, Ag7P3SII, Ag4P2S7 Ag2P2S6. .
  相似文献   

16.
The influence of co-ions in the eluent on the separation factor () of lithium isotope separation has been studied by ion exchange chromatography. A strongly acid cation exchange resin (Dowex 50W-X8) was used for the separation of lithium isotopes. The co-ions used in eluent were H+, K+, Ba2+, Cu2+, Al3+ and Cr3+ as their chlorides. From the experiments, it was found that6Li was enriched in the resin phase and7Li in solution phase. At the same distribution coefficient (Kd=30), the separation factor increased linearly with the charge of co-ion (=1.0022 to 1.0039).  相似文献   

17.
Résumé La migration des ions cadmium, cuivre-II, bismuth, arsenic-III, antimoine-III, étain-II, fer-III, aluminium, chrome-III, cobalt, nickel, manganèse et zinc, en présence d'acide ,-diaminodiéthyléther-N,N tétracétique, a été étudiée en fonction du pH. Des nombreuses séparations sont possibles.
Summary The migration of the following ions in the presence of, -diaminodiethylether-N,N-tetraacetic acid has been studied in relation to the pH: Cd, Cu(II), Bi, As(III), Sb(III), Sn(II), Fe(III), Al, Cr(III), Co, Ni, Mn, Zn. Many separations are possible.

Zusammenfassung Die Abhängigkeit der elektrophoretischen Wanderung der Ionen Cd2+, Cu2+, Bi3+, As3+, Sb3+, Sn2+, Fe3+, Al3+, Cr3+, Co2+, Ni2+, Mn2+ und Zn2+ vom pH bei Gegenwart von,-Diaminodiäthyläther-N,N-tetraessigsäure wurde untersucht. Die Möglichkeit zahlreicher Trennungen ist gegeben.


Dédié à Monsieur le professeurF. Feigl, à l'occasion de son 70e anniversaire.  相似文献   

18.
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.
  相似文献   

19.
Kinetics of metal exchange reaction Cd(II) Zn(II) and Cd(II) Cu(II) in Cd complexes with tetraphenylporphyrin in DMSO is studied. Reaction with Cu(II) nitrate occurs in both cases more vigorously as compared to that with Zn(II) nitrate. Conditions for metal exchange reactions are studied depending on the nature of metal porphyrinate, a salt (nitrates, acetates, and chlorides of Zn(II), Cu(II), and Co(II), and of organic solvent (DMSO, CH3CN). It is shown that Zn(II) complexes with nonplanar porphyrins do not show metal exchange Zn(II) Cu(II) or Zn(II) Co(II) under mild conditions in DMSO and CH3CN.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 104–109. Original Russian Text Copyright © 2005 by D. Berezin, Shukhto, Nikolskaya, B. Berezin.  相似文献   

20.
A cross-linked agarose (Novarose) support was chemically modified with a novel salen-type Schiffs base; 2,2-[1,2-ethandiyl bis(nitrilimethylidyne)] bis(orthocresol) and was used to develop an efficient, simple and low-cost method for matrix separation and preconcentration of lead in water. The binding capacity of the adsorbent, packed in a 6.5mm i.d. glass column, was tested for different metal ions, and a capacity of 4973 (±95) µg per mL of packed adsorbent for triplicate measurements was obtained for lead at pH 6.0.The effects of pH, ionic strength, buffer concentration, sample volume, eluent concentration and volume, and matrix ions on the column recovery of Pb2+ were carefully studied. Quantitative recoveries were obtained for the analyte in a pH range of 5.5 to 7.0. Enrichment volumes up to 300mL and ionic strengths up to 0.5molL–1 had no significant effect on the recovery of Pb2+. The method also tolerated relatively high concentrations of matrix ions such as Ca2+, Mg2+, Fe3+, Cu2+, Zn2+, Mg2+ and Cd2+ with no considerable effect on the analytes signal. A few mL of 0.4molL–1 hydrochloric acid was sufficient for quantitative elution of the analyte from a 0.5mL column before its flame AAS determination. Preconcentration factors up to 60 and a detection limit of 2.5µgL–1 were obtained for the method. The precision, expressed as relative standard deviation, was 2.9% (at 100µgL–1) calculated from six replicate measurements. The method was successfully applied to the determination of Pb2+ in some river and spiked river water samples with good precision.  相似文献   

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