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61.
Zbigniew Gregorowicz Henryk Jalowiecki und Franciszek Buhl 《Fresenius' Journal of Analytical Chemistry》1967,233(5):346-348
Zusammenfassung Eine gravimetrische Methode zur Bestimmung von Quecksilber(I)-ionen mit Kaliumhydrogenphthalat wurde ausgearbeitet. Bei Konzentrationen von 0,1–0,2 g HgI/100 ml sind die Analysenergebnisse gut reproduzierbar. Die mittleren Abweichungen liegen zwischen –0,1 und –0,2%. Die Bestimmung wird durch Ag+, Pb2+, Hg2+, Bi3+, Fe3+ sowie Anionen, die mit Quecksilber(I) unlösliche Niederschläge bilden, gestört.
Summary A gravimetric method for the determination of mercury(I) ions by means of o-phthalate is described. For concentrations of 0.1 to 0.2 g HgI/100 ml well reproducible results are obtained. The mean deviations of the single determinations vary between –0.1 and –0.2%. Ag+, Pb2+, Hg2+, Bi3+, Fe3+ and anions forming sparingly soluble precipitates with mercurous ions interfere with the determination.相似文献
62.
Marek Rakowski 《Integral Equations and Operator Theory》1991,14(4):564-585
We define the pseudoinverse (resp. a generalized pseudoinverse) of a matrix-valued functionF to be the functionF
x such that, for each in the domain ofF, F
x () is the inverse (resp. a generalized inverse) of the matrixF(). We derive a state space formula for a generalized pseudoinverse of a rational matrix function without a pole or zero at infinity. This derivation makes use of the theorem characterizing the factorization of a nonregular rational matrix functionW in terms of the decomposition of the state space of a realization ofW. We also give a formula for a generalized pseudoinverse of an arbitrary rational matrix function in the form of a centered realization. We indicate some applications of generalized pseudoinverses of matrix valued functions. 相似文献
63.
Franciszek Herold Jerzy Kleps Beata Szczsna Romana Anulewicz‐Ostrowska 《Journal of heterocyclic chemistry》2002,39(4):773-782
A series of new 4‐aryloctahydropyrido[1,2‐c]pyrimidine‐1,3‐diones 6a,b,d‐h and j were synthesized by intramolecular cyclization of α‐aryl‐α‐(1‐ethoxycarbonyl‐2‐piperidyl)‐acetamide derivatives 5a,b,d‐h and j . The structures of compounds were determined by 1H and 13C nmr spectroscopy. Nmr and X‐ray diffraction data indicate that the configuration at the C4, C4a stereocenters constitute RR and SS pair. 相似文献
64.
Speciation of vanadium in soil 总被引:1,自引:0,他引:1
A method for speciation of vanadium in soil is presented in this work. The sequential extraction analysis procedure of Tessier et al. for heavy metals was used for the vanadium separation. The method consists of sequential leaching of the soil samples to separate five fractions of metals: (1) exchangeable, (2) bound to carbonates, (3) bound to Fe-Mn oxides, (4) bound to organic matter and (5) residual. The leaching solutions of Tessier were used for the vanadium extraction, only for the residual fraction the HClO4 was replaced with H2SO4. The optimum conditions for leaching of vanadium from soil (weight of sample, concentration and volume of extractants, time of extraction) were chosen for each fraction. A sensitive, spectrophotometric method based on the ternary complex V(IV) with Chrome Azurol S and benzyldodecyldimethylammonium bromide (ε=7.1×104 l mol−1 cm−1) was applied for the vanadium determination after separation of V(V) by solvent extraction using mesityl oxide and reduction of V(V) using ascorbic acid. This method was applied for vanadium speciation in soil from two different regions of Poland: Upper Silesia (industrial region) and Podlasie (agricultural region). The content of vanadium in the fractions of Upper Silesia soil was respectively (in 10−3%): I, 3.39; III, 4.53; IV, 10.70; V, 8.70 and it was the highest in the organic fraction, indicating input by anthropogenic activities. The content of vanadium in Podlasie soil was clearly lower and it was (in 10−3%): I, 2.07; III, 0.92; IV, 0.69; V, 1.23. The concentration of vanadium in fraction 2 of both soils was less than detection limit of applied method. The total content of vanadium in the five soil fractions was in good correlation with the total content of this element in both soils found after HF-H2SO4 digestion. Analysis using the ICP-AES method gave comparable results. 相似文献
65.
Curtis CJ Miedaner A Ciancanelli R Ellis WW Noll BC Rakowski DuBois M DuBois DL 《Inorganic chemistry》2003,42(1):216-227
The reaction of Et(2)PCH(2)N(Me)CH(2)PEt(2) (PNP) with [Ni(CH(3)CN)(6)](BF(4))(2) results in the formation of [Ni(PNP)(2)](BF(4))(2), which possesses both hydride- and proton-acceptor sites. This complex is an electrocatalyst for the oxidation of hydrogen to protons, and stoichiometric reaction with hydrogen forms [HNi(PNP)(PNHP)](BF(4))(2), in which a hydride ligand is bound to Ni and a proton is bound to a pendant N atom of one PNP ligand. The free energy associated with this reaction has been calculated to be -5 kcal/mol using a thermodynamic cycle. The hydride ligand and the NH proton undergo rapid intramolecular exchange with each other and intermolecular exchange with protons in solution. [HNi(PNP)(PNHP)](BF(4))(2) undergoes reversible deprotonation to form [HNi(PNP)(2)](BF(4)) in acetonitrile solutions (pK(a) = 10.6). A convenient synthetic route to the PF(6)(-) salt of this hydride involves the reaction of PNP with Ni(COD)(2) to form Ni(PNP)(2), followed by protonation with NH(4)PF(6). A pK(a) of value of 22.2 was measured for this hydride. This value, together with the half-wave potentials of [Ni(PNP)(2)](BF(4))(2), was used to calculate homolytic and heterolytic Ni-H bond dissociation free energies of 55 and 66 kcal/mol, respectively, for [HNi(PNP)(2)](PF(6)). Oxidation of [HNi(PNP)(2)](PF(6)) has been studied by cyclic voltammetry, and the results are consistent with a rapid migration of the proton from the Ni atom of the resulting [HNi(PNP)(2)](2+) cation to the N atom to form [Ni(PNP)(PNHP)](2+). Estimates of the pK(a) values of the NiH and NH protons of these two isomers indicate that proton migration from Ni to N should be favorable by 1-2 pK(a) units. Cyclic voltammetry and proton exchange studies of [HNi(depp)(2)](PF(6)) (where depp is Et(2)PCH(2)CH(2)CH(2)PEt(2)) are also presented as control experiments that support the important role of the bridging N atom of the PNP ligand in the proton exchange reactions observed for the various Ni complexes containing the PNP ligand. Similarly, structural studies of [Ni(PNBuP)(2)](BF(4))(2) and [Ni(PNP)(dmpm)](BF(4))(2) (where PNBuP is Et(2)PCH(2)N(Bu)CH(2)PEt(2) and dmpm is Me(2)PCH(2)PMe(2)) illustrate the importance of tetrahedral distortions about Ni in determining the hydride acceptor ability of Ni(II) complexes. 相似文献
66.
67.
Zuzanna Molęda Anna Zawadzka Małgorzata Żytek Daria Madej Franciszek Pluciński Jan K. Maurin Zbigniew Czarnocki 《Comptes Rendus Chimie》2013,16(9):807-813
A series of carbamate melatonin derivatives was treated with performic acid, providing tricyclic products with a 3-hydroxytetrahydropyrrolo[2,3-b]indole skeleton. An unusual migration of carbamate groups was observed in some cases, and the reaction appeared to be strongly dependent on the type of substituent in the phenyl ring of the phenylcarbamate group. Theoretical calculations suggest that the reaction is kinetically controlled. 相似文献
68.
Adam Rakowski 《Colloid and polymer science》1911,9(5):225-230
Ohne Zusammenfassung 相似文献
69.
Liu T Chen S O'Hagan MJ Rakowski DuBois M Bullock RM DuBois DL 《Journal of the American Chemical Society》2012,134(14):6257-6272
The iron complexes CpFe(P(Ph)(2)N(Bn)(2))Cl (1-Cl), CpFe(P(Ph)(2)N(Ph)(2))Cl (2-Cl), and CpFe(P(Ph)(2)C(5))Cl (3-Cl)(where P(Ph)(2)N(Bn)(2) is 1,5-dibenzyl-1,5-diaza-3,7-diphenyl-3,7-diphosphacyclooctane, P(Ph)(2)N(Ph)(2) is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane, and P(Ph)(2)C(5) is 1,4-diphenyl-1,4-diphosphacycloheptane) have been synthesized and characterized by NMR spectroscopy, electrochemical studies, and X-ray diffraction. These chloride derivatives are readily converted to the corresponding hydride complexes [CpFe(P(Ph)(2)N(Bn)(2))H (1-H), CpFe(P(Ph)(2)N(Ph)(2))H (2-H), CpFe(P(Ph)(2)C(5))H (3-H)] and H(2) complexes [CpFe(P(Ph)(2)N(Bn)(2))(H(2))]BAr(F)(4), [1-H(2)]BAr(F)(4), (where BAr(F)(4) is B[(3,5-(CF(3))(2)C(6)H(3))(4)](-)), [CpFe(P(Ph)(2)N(Ph)(2))(H(2))]BAr(F)(4), [2-H(2)]BAr(F)(4), and [CpFe(P(Ph)(2)C(5))(H(2))]BAr(F)(4), [3-H(2)]BAr(F)(4), as well as [CpFe(P(Ph)(2)N(Bn)(2))(CO)]BAr(F)(4), [1-CO]Cl. Structural studies are reported for [1-H(2)]BAr(F)(4), 1-H, 2-H, and [1-CO]Cl. The conformations adopted by the chelate rings of the P(Ph)(2)N(Bn)(2) ligand in the different complexes are determined by attractive or repulsive interactions between the sixth ligand of these pseudo-octahedral complexes and the pendant N atom of the ring adjacent to the sixth ligand. An example of an attractive interaction is the observation that the distance between the N atom of the pendant amine and the C atom of the coordinated CO ligand for [1-CO]BAr(F)(4) is 2.848 ?, considerably shorter than the sum of the van der Waals radii of N and C atoms. Studies of H/D exchange by the complexes [1-H(2)](+), [2-H(2)](+), and [3-H(2)](+) carried out using H(2) and D(2) indicate that the relatively rapid H/D exchange observed for [1-H(2)](+) and [2-H(2)](+) compared to [3-H(2)](+) is consistent with intramolecular heterolytic cleavage of H(2) mediated by the pendant amine. Computational studies indicate a low barrier for heterolytic cleavage of H(2). These mononuclear Fe(II) dihydrogen complexes containing pendant amines in the ligands mimic crucial features of the distal Fe site of the active site of the [FeFe]-hydrogenase required for H-H bond formation and cleavage. 相似文献
70.
Mahdi Hormozi Franciszek Prus-Wiśniowski Hjalmar Rosengren 《Journal of Mathematical Analysis and Applications》2014
The characterization of the inclusion of Waterman–Shiba spaces ΛBV(p) into generalized Wiener classes of functions BV(q;δ) is given. It uses a new and shorter proof and extends an earlier result of U. Goginava. 相似文献