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1.
Summary The ternary Cu2+-Ni2+-citrate (cit3–) system was investigated potentiometrically in aqueous solution, at different temperatures, 10t45°C, and ionic strengths, 0.03I0.8 mol dm–3, using potassium nitrate or tetraethylammonium bromide as background salt. Since the citrate anion forms weak complexes with potassium, the stability constants here reported differ according to whether the potassium association is considered or not. In the presence of both Cu2+ and Ni2+, the mixed metal species, [CuNi(cit)2H–2]4– is formed with citrate in solution, in addition to the various binary complexes. We have obtained the dependence for all the formation constants on ionic strength and temperature. The previous suggestions concerning a general equation for describing the dependence, log =f(I), are confirmed; from the study of log =f(T) we have obtained the values of thermodynamic parameters. The dependence of H on ionic strength is discussed.  相似文献   

2.
The influence of the preparation method (i.e., Pd precursor and heat treatments) on the reduction pattern of Pd/-Al2O3 catalysts has been investigated by TPR. The role of the Cl ions and the effect of metal dispersity on the stability of Pd catalysts reduced at different Tr (400Tr800°C) have been discussed. Reoxidation of Pdo occurs during exposure to the atmosphere and the formation both of easily reducible PdO forms and Cl-containign Pd2+ oxo-complexes, strongly interacting with alumina surface, has been pointed out.  相似文献   

3.
A Bayard-Alpert (BA) gauge was used to determine apparent relative sensitivites Srel,X for O2, N2O, NO, NO2, NH3, CClF3 and CH3OH from gauge calibration measurements in the range 1.3×10–1 Pap1.3·10–3Pa. Nitrogen was used as a calibration standard.  相似文献   

4.
A detailed investigation of the oxidation of L-ascorbic acid (H2A) by the title complex has been carried out using conventional spectrophotometry at 510 nm, over the ranges: 0.010 [ascorbate] T 0.045 mol dm–3, 3.62 pH 5.34, and 12.0 30.0 °C, 0.50 I 1.00 mol dm–3, and at ionic strength 0.60 mol dm–3 (NaClO4). The main reaction products are the bis(pyridine-2,6-dicarboxylate)cobaltate(II) ion and l-dehydroascorbic acid. The reaction rate is dependent on pH and the total ascorbate concentration in a complex manner, i.e., k obs = (k 1 K 1)[ascorbate] T /(K 1 + [H+]). The second order rate constant, k 1 [rate constant for the reaction of the cobalt(III) complex and HA] at 25.0 °C is 2.31 ± 0.13 mol–1 dm3 s–1. H = 30 ± 4 kJ mol–1 and S = –138 ± 13 J mol–1 K–1. K 1, the dissociation constant for H2A, was determined as 1.58 × 10–4 mol dm–3 at an ionic strength of 0.60 mol dm–3, while the self exchange rate constant, k 11 for the title complex, was determined as 1.28 × 10–5 dm3 mol–1 s–1. An outer-sphere electron transfer mechanism has been proposed.  相似文献   

5.
Zusammenfassung Die Charakterisierung von Kohlenstoff- und Schwefelverbindungen in korngrößenseparierend gesammelten Staubproben wird durch temperaturprogrammierte Zersetzung der Probe im Sauerstoffstrom und simultane Analyse von gebildetem CO2 und SO2 durchgeführt. Eine Unterscheidung von zwei organischen Kohlenstofffraktionen sowie von »Ruß-Kohlenstoff«, »Carbonatkohlenstoff«, »Konversionsschwefel«, »Ruß-Schwefel« und »Schwefel aus thermisch stabilen Sulfaten« in vier Korngrößenbereichen im Staubkollektiv 0,1–25 m AD ermöglicht die Zuordnung bestimmter Verbindungsgruppen zu verschiedenenen Bereichen des »Multimodalen Modells«. Zur Analyse werden 50–200 g Probe benötigt. Der Analysator besteht aus der Kombination eines temperaturprogrammierten Ofens mit gasanalytischen Monitoren für CO2 und SO2. Die Nachweisempfindlichkeit liegt bei 40 ng S s–1 und 400 ng C s–1 für vollen Schreiberausschlag (200 mm). In Anwendungsbeispielen wird der Einsatz der Methode zur Quellenanalyse von Aerosolen demonstriert.
Thermo gas-analyzer for the characterization of carbonaceous and sulphurous compounds in atmospheric particles
Summary Characterization of carbonaceous and sulphurous compounds in size fractions of atmospheric particles is carried out by temperature programmed decomposition of the sample in oxygen atmosphere and simultaneous detection of evolved CO2 and SO2. The speciation of two organic carbon fractions, of soot carbon, carbonate carbon, converted sulphur, soot sulphur and sulphur from thermally stable sulphates in four size ranges of atmospheric particles (0.1–25 m AD) makes possible the classification into modes according to the multimodal model. For the analysis 50–200 g of sample is required. The analyzer, a combination of a temperature programmed furnace with instruments for monitoring of CO2 and SO2 is operated with a sensitivity of 40 ng S s–1 and 400 ng Cs–1 for recorder full-scale (200mm). Results of field tests demonstrate the application for aerosol source identification and conversion studies.
Der Autor möchte Herrn Prof. Dr. H. Malissa für die Anregungen und Diskussionen zur vorliegenden Arbeit vielmals danken. Mein Dank gilt auch Frl. Ing. Ch. Minich für die technische Assistenz bei der Durchführung der Analysen.Diese Arbeit wurde durch Mittel und Geräte des Bundesministeriums für Gesundheit und Umweltschutz unterstützt.  相似文献   

6.
In order to extend the energy range of the systematic investigation on relative thick target yields performed by ANTTILA et al2 for 1Ep2.4 MeV bombarding energies, gamma spectra and yield data are presented for elements Z=3–9, 11–17, 19–21 in the energy range 2.4Ep4.2 MeV and the results are discussed from the point of view of PIGE analysis.  相似文献   

7.
A number of 1-vinylpyrroles were studied by PMR spectroscopy. Bulky substituents in the position of the pyrrole ring give rise to deshielding of hb and a decrease in2J(HA,HB) and6J(H3,HB). The results were interpreted as a decrease in the p, conjugation in the N-vinyl group due to distortion of the coplanarity. The dihedral angle () between the planes of the pyrrole ring and the double bond was estimated (with an accuracy of ±5 °).See [10] for our previous communication [10].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 328–330, March, 1980  相似文献   

8.
Summary The reversible complex formation between 2-(2-aminoethyl) benzimidazole (AEB) and nickel(II) was studied by stopped flow spectrophotometry at I = 0.30 mol dm–3. Both the neutral and monoprotonated form of AEB reacted to give the NiAEB2+ chelate. At 25 °C, the rates and activation parameters for the reactions NiII + AEB NiAEB2+ and NiII + AEBH+ NiAEB2+ + H+ are k f L(dm–3 mol–1 s–1) = (2.17 ± 0.24) × 103, H (kJ mol–1) = 40.0 ± 0.8, S (JK–1 mol–1) = – 47 ± 3 and k inff pHL (dm3 mol–1 s–1) = 33 ± 10, H (kJ mol–1) = 42.0 ±2.7, S (JK–1 mol–1) = – 72 ± 9. The dissociation of NiAEB2+ was acid catalysed and k obs for this process increased linearly with [H+] in the 0.01–0.15 mol dm–3 (10–30 °C) range with k H(dm3 mol–1s–1) (25 °C) = 329 ± 6, H (kJ mol–1) = 40 ± 2 and S (JK–1 mol–1) = – 61 ± 8. The results also indicated that the formation of NiAEB2+ involves a chelation-controlled, rate-limiting process. Analysis of the S ° data for the acid ionisation of AEBH inf2 p2+ and the formation of NiAEB2+ showed that the bulky AEBH+ ion has a solvent structure breaking effect as compared to AEB [s aqS ° (AEBH+) – s aq ° (AEB) = 69 JK–1 mol–1], while AEBH inf2 p2+ is a solvent ordering ion relative to NiAEB2+ [s aq° (NiAEB2+) – ovS aq ° (AEBH inf2 p2+ ) = 11 JK–1 mol–1].Author to whom all correspondence should be directed.  相似文献   

9.
Six cardenolides have been isolated from the leaves ofAcokanthera venenata G. Don: AV-1, mp 252–255°C, [] D 20 +39.4° (MeOH); AV-2, mp 199–208°C, [] D 20 -59.3° (MeOH); AV-3, mp 269–275°C/300–304°C, [] D 21 –69.8° (MeOH); AV-4, mp 279–289°C; AV-5, mp 222–225°, [] D 20 -64.3° (MeOH); and AV-6, mp 193–196°C [] D 20 –23.8° (MeOH — CHCl3). AV-5 has been identified as acovenoside A. AV-3 is a new cardiac glycoside: it is 1-acetoxy-3-(4-O--D-glucosyl-3-O-methyl--L-talomethylosyloxy)-14-hydroxy-5, 14-card-20(22)-enolide (glucoacovenoside B).Khar'kov State Pharmaceutical Institute. All-Union Scientific Research Institute of Drug, Chemistry and Technology, Khar'kov. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 372–376, May–June, 1987.  相似文献   

10.
Zusammenfassung Der lineare thermische Ausdehnungskoeffizient von linearem Polyäthylen hoher Dichte wurde im Temperaturbereich –20 °C bis + 40°C bestimmt. Bei isotropen Proben besteht eine lineare Beziehung zwischen Dichte bzw. Kristallisationsgrad v und. Die gemessenen Koeffizienten liegen fürT 0 = 20 °C im Bereich = 110 ... 130 · 10–6 K–1.Kalt verstreckte Proben mit Verstreckungsgraden = 8 ... 15 haben beiT 0 = 20 °C in Verstreckrichtung den Koeffizienten l = –24 · 10–6 K–1. Der negative Zahlenwert von tl ist unabhängig von und weiteren Herstellungsparametern. Seine Ursache ist einerseits die Orientierung derc-Achsen der Kristallite in Verstreckrichtung mit c = –12 · 10–6 K–1 und andererseits der negative Koeffizient am * –50 · 10–6 K–1 der verspannten amorphen Phase, der auf dem gummielastischen Verhalten der tie-molecules beruht.Beim Tempern oberhalb von +40 °C schrumpfen die Proben irreversibel, wobei | ansteigt und nach dem Aufschmelzen der Proben wieder den Wert des isotropen Materials annimmt. Nach dem Tempern wenig unterhalb der Schmelztemperatur der Kristallite wurden überhöhte Koeffizienten | gemessen, die eine Rotation der Kristallite um dieb-Achsen erkennen lassen.
Summary The linear thermal coefficient of expansion,, of high density linear polyethylene has been determined in the temperature range of –20 ° ... + 40 °C. For isotropic samples a linear relationship between density or crystallinity v and is valid. Measured values of forT 0 = 20 °C amount to = 110 ... 130 · 10–6 K–1.Cold drawn samples of draw ratios = 8 ... 15 yield | = –24 · 10–6 K–1 atT 0 = 20 °C parallel to the draw axis. The negative value of | does not depend on draw ratio or other parameters of sample processing. It is caused byc-axis orientation of the crystallites in draw direction with c = –12 · 10–6 K–1 and by a negative coefficient am * = –50 · 10–6 K–1 of the stressed amorphous phase, which is due to rubber elastic behaviour of the tie molecules.When annealed above 40 °C the samples shrink irreversibly and | is augmented. After melting the samples the value of isotropic material is restored. Annealing the samples little below the melting temperature of the crystallites leads to superelevated values all which reflect| rotation of the crystallites around theb-axis.
  相似文献   

11.
Summary The adiabatic corrections of thei 3g state of H2 are calculated for a wide range of internuclear distances using an explicitly correlated wavefunction. The vibrational structure of this state is calculated in the adiabatic approximation. It is shown that forN=1 levels of the – substate, for which the nonadiabatic corrections are negligible, the agreement between theory and experiment is excellent; the small mass independent discrepancy of the order of 0.5–3 cm–1 is due to the convergence error in the Born-Oppenheimer calculations. For higherN the discrepancy is much larger. However, it is mass andN-dependent and it is almost entirely due to the nonadiabatic effects caused by3g-3g interactions. The still larger discrepancy for the + substate of thei state is evidently caused by additional interactions of thei state with close-lying states of3 g + symmetry.Dedicated to Prof. Klaus Ruedenberg on the occasion of his 70th birthday  相似文献   

12.
A method for the determination of aldrin, dieldrin, DDT, DDE, and DDD contamination in animal fats (beef tallow, lard, and chicken fat) without using toxic reagents is developed, that uses high-performance liquid chromatography after the sample has been prepared by matrix solid-phase dispersion (MSPD) with acidic alumina oxide. A reversed-phase C1-silica column with a mobile phase of 50% (v/v) ethanol solution (in water) and a photo-diode array detector were used for the determination. Average recoveries of the target compounds (0.2–5.0 g g–1) ranged from 84–98%, with coefficients of variation of <5%. The limits of quantitation were 0.16 g g–1 for AD, 0.10 g g–1 for DD, 0.06 g g–1 for DDT, 0.07 g g–1 for DDE, and 0.05 g g–1 for DDD. No toxic reagents were used at all.  相似文献   

13.
Active silica gel phase (I) was chemically modified to the corresponding amino- (SiNH2) and chloro- (SiCl) derivatives via silylation reactions. These were used to synthesize two newly modified silica gel phases (II, III) by direct chemical reaction with 2-hydroxynaphthaldehyde (2-HNA). The surface coverage values are 370, 432µmolg–1 and 320, 355µmolg–1 for (II) and (III), on the basis of thermal desorption and metal probe testing method, respectively. The metal sorption properties of silica gel phases (II, III) were studied and compared with active silica gel phase (I). The maximum determined metal capacity values were found to be 10–110, 20–290 and 20–370µmolg–1 for phases I, II and III, respectively. The distribution coefficient values (Kd) were also determined for a series of metal ions, and the results showed that the two new chemically modified phases (II and III) were highly selective for Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+. The potential applications of silica gel phases (II, III) as solid phase extractors for the same five metal ions spiked in drinking tap water (1.000µgmL–1) were found to give percentage recovery values in the range of 90.2–96.3±4.1–6.3%, while pre-concentration of the same five metal ions spiked in drinking tap water (50.0ngmL–1) was successfully accomplished with a percentage recovery range of 92.6–95.8±4.8–5.7%.Received December 16, 2002; accepted May 14, 2003 published online September 1, 2003  相似文献   

14.
The stability constans, 1, of each monochloride complex of Eu(III) have been determined in the methanol and water mixed system with 1.0 mol·dm–3 ionic strength using a solvent extraction technique. The values of 1 increase with an increase in the mole fraction of methanol (X S ) in the mixed solvent system when 0X S 0.40. The, distance of Eu3+–Cl in the mixed solvent system was calculated using the Born-type equation and the Gibbs' free energy derived from 1. Calculation of the Eu3+–Cl distance and the preferential solvation, of Eu3+ by water proposed the variation of the outersphere complex of EuCl2+ as follows: (1) [Eu(H2O)9]3+Cl, [Eu(H2O)8]3+Cl and [Eu(H2O)7(CH3OH)3+Cl inX S0.014, (2) [Eu(H2O)8]3–Cl and [Eu(H2O)7(CH3OH)]3+Cl in 0.014<X S <0.25 and (3) [Eu(H2O)7(CH3OH)]3–Cl and [Eu(H2O)6(CH3OH)[2 3+Cl in 0.25<X S 0.40.  相似文献   

15.
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   

16.
Mössbauer spectroscopy was used to study hyperfine interactions on 57Fe nuclei of SrCo1 – y Fe y O3 – z solid solutions (0.2 y 0.8). The 57Fe spectra measured in the paramagnetic temperature range look like a superposition of two quadrupole doublets whose parameters correspond to high-spin Fe4+cations ( = 0.1 mm/s; = 0.4 mm/s) in the anion surrounding with coordination number 5 (tetragonal pyramid) and to Fe3+cations ( = 0.3 mm/s; = 0.4 mm/s) in the distorted octahedral environment. The relative number and pattern of distribution of heterovalent cations (Co4+, Co3+, Fe4+, and Fe3+) in the B-sublattice of perovskites were determined. The values of the electronic exchange constants in the solid solutions obtained through Mössbauer spectroscopy were compared with those obtained from thermodynamic calculations. The oxygen penetration in perovskites was found to depend on their composition and structure.  相似文献   

17.
Summary. Ab initio multireference and coupled cluster methods (MR-SDCI(+Q), CASPT2, CCSD(T)) and density functional theory methods (B3LYP, MPWPW91) have been applied to examine geometrical structures and vibrational frequencies of noble gas (Ng) – transition metal compounds, Ng–NiCO, Ng–NiN2, and Ng–CoCO (Ng = He, Ne, Ar, Kr, Xe). It is shown that the respective compounds can have a larger binding energy than a typical van der Waals interaction energy. The binding mechanism is explained by a partial electron transfer from a noble gas atom to the low-lying 4s and 3d vacant orbitals of the transition metal atom. Theoretical calculations show that the binding of noble gas atom results in a large shift of the bending frequency: 361.1cm–1 (NiCO) to 403.5cm–1 (Ar–NiCO); 308.5cm–1 (NiN2) to 354.8cm–1 (Ar–NiN2); 373.0cm–1 (CoCO) to 422.6cm–1 (Ar–CoCO). The corresponding experimental frequencies determined in solid argon are 409.1cm–1 (NiCO), 357.0cm–1 (NiN2), and 424.9cm–1 (CoCO), which are much closer to the corresponding frequency of Ar–NiCO, Ar–NiN2, and Ar–CoCO, respectively.  相似文献   

18.
A selective and sensitive method for the extraction and microgram determination of molybdenum (VI) with hydroxamic acid as yellow molybdenum-hydroxamate complex from acidic medium is described. The molybdenum-PCPPSAHA complex has max 388 nm, molar absorptivity 5.0 × 103l mol–1 cm–1. The system obeys Beer's law in the range of 1–28 g/ml of molybdenum(VI). Sandell's sensitivity is 0.0192 g cm2 and stoichiometry of the complex is 12, molybdenum: PCPPSAHA while mixed complex molybdenum-PCPPSAHA-morin has max 400 nm and molar absorptivity 5.9 × 103lmo1–1 cm–1 and stoichiometry of the complex is 121.The molybdenum is determined by graphite furnace atomic absorption spectrophotometry after directly pipetted the extract into the furnace which increases the sensitivity 20 fold.  相似文献   

19.
A cluster structure of the surface of a polypyromellitimide film was studied by the electron microscopy and ATR IR spectroscopy methods at different steps of consecutive treatment with aqueous solutions of an alkali and acid. The effective size and fractal dimension D of polyamidoacid clusters, as well as the degree s of the filling of the surface with the latter were calculated from the data of the electron microscopy as a function of the degree of imide group conversion into amidoacid units on the film surface. The s and D parameters were shown to increase with a rise in : s = 0.1–0.3 and D = 1.3–1.4 at < cr and s 0.6 and D 1.7 at > cr, where cr is a critical degree of conversion, which corresponds to the formation of a continuous physical network of polyamidoacid macromolecules or a percolation cluster. In a region close to cr (at < cr), the correlation length land the concentration C of the clusters vary according to the laws of the percolation theory for two-dimensional lattices: l (cr – ) and C (cr – ), where = 1.3 ± 0.1 and = 0.67 ± 0.05.  相似文献   

20.
The glycosylation of 3,12-diacetoxy-20(S),24(R)-epoxydammaran-25-ol with -acetobromoglucose under the conditions of Helferich's modification and with D-glucose tert-butyl orthoacetate under the conditions of the orthoester method gives a high yield (60–64%) of the hexacetate of the -D-glucoside at the tertiary hydroxy group of 20(S),24(R)-epoxydammarane-3,12,25-triol (III) with mp 207–209°C (ethanol), [] D 20 -20.9 (c 1.0, CHCl3). Saponification with 10% KOH in methanol gives the free 20(S),24(R)-epoxydammarane-3,12,25-triol 25-O--D-glucoside (V) (yield 90%) with mp 275–279°C (methanol), [] D 20 +11.4° (c, 1.0, C5H5). The results of IR and1H and13C NMR spectroscopy and of elementary analysis are given.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 205–208, March–April, 1980.  相似文献   

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