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1.
The solubilities of NpO2(s) in the KURT (KAERI Underground Research Tunnel) granitic groundwater with low ionic strength were measured experimentally and calculated by a geochemical code. Then these results were compared with each other as well as with foreign results. The concentrations of neptunium were measured as 6·10−8−2·10−8 mol/L at a pH = 9.5–11.1 and Eh = −0.2 V, and less than 5·10−9 mol/L at a pH = 11.8–13.0 and Eh = −0.3–0.44 V. The dominant aqueous species were presumed as Np(OH)x(CO3)y 4−x−2y complexes and Np(OH)4(aq) at pH = 9.5–13 under the Eh<−0.2 V reducing condition.  相似文献   

2.
2-Formylpyridine semicarbazone L reacts with cobalt, nickel, copper and zinc chlorides, nitrates and perchlorites to form coordination compounds of compositions ML2X2·nH2O (M=Co, Ni, Cu, Zn; X = Cl, NO3, ClO4; L = NC5H4-CH=N-NH-C(O)-NH2; n = 0, 1) and CuLX2·nH2O (X = Cl, Br, NO3; n = 0−0.5). Complex CuL(NO3)2 has polynuclear, CuLX2·0.5H2O (X = Cl, Br), binuclear, and other compounds, mononuclear structures. Azomethine L behaves in them as tridental N,N,O-ligand. Thermolysis of these complexes proceeds through such stages as dehydration (80–95°C), deactivation (145–155°C) and complete theral degradation (170–590°C). Complexes CuLX2·nH2O (X = Cl, NO3; n = 0−0.5) were established to inhibit in vitro the growth and reproduction of 100% of cancer cells of human mieloid leukaemia HL-60 at 10−4 M concentration. At 10−5 M concentration they inhibit only 10% of cells, and at 10−6 M concentration they do not possess anticancer activity.  相似文献   

3.
The radiation chemical redox transformations in solutions of bromides in the presence of minor additives of iodides were studied by pulse radiolysis. The change in the concentrations of the Br and I ions changes the ratio of the formed short-lived radical anions Br2 ·−, BrI·−, and I2 ·−. The spectrum of the mixed radical anion BrI·− contains a broad optical band at 370 nm with ɛ370 = 9650 L mol−1 cm−1. The reduction potential of the BrI·−/Br, I pair is 1.25 V. The rate constants for the forward and backward reactions Br2 ·− + I ⇌ BrI·− + Br are k f = 4.3·109 and k r = 1.0·105 L mol−1 s−1, respectively; for the reactions BrI·− ⇌ Br + I·, k f = 5.7·108 s−1 and k r = 1.0·1010 L mol−1 s−1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1787–1792, September, 2008.  相似文献   

4.
Solubility product (Lu(OH)3(s)⇆Lu3++3OH) and first hydrolysis (Lu3++H2O⇆Lu(OH)2++H+) constants were determined for an initial lutetium concentration range from 3.72·10−5 mol·dm−3 to 2.09·10−3 mol·dm−3. Measurements were made in 2 mol·dm−3 NaClO4 ionic strength, under CO2-free conditions and temperature was controlled at 303 K. Solubility diagrams (pLuaq vs. pC H) were determined by means of a radiochemical method using 177Lu. The pC H for the beginning of precipitation and solubility product constant were determined from these diagrams and both the first hydrolysis and solubility product constants were calculated by fitting the diagrams to the solubility equation. The pC H values of precipitation increases inversely to [Lu3+]initial and the values for the first hydrolysis and solubility product constants were log10 β* Lu,H = −7.92±0.07 and log10 K*sp,Lu(OH)3 = −23.37±0.14. Individual solubility values for pC H range between the beginning of precipitation and 8.5 were S Lu3+ = 3.5·10−7 mol·dm−3, S Lu(OH)2+ = 6.2·10−7 mol·dm−3, and then total solubility was 9.7·10−7 mol·dm−3.  相似文献   

5.
The nature of intermediate species and their reactions were studied by laser pulse photolysis for a photochromic system consisting of 8,8′-diquinolyl disulfide (RSSR) and a planar NiII complex di(mercaptoquinolinato)nickel(II) (Ni(SR)2) in toluene and benzene solutions. Under exposure to laser radiation, disulfide RSSR dissociates to two RS· radicals, whose spectrum has an intense absorption band with a maximum at λ = 400 nm (ε = 8400 L mol−1 cm−1). The radicals disappear by recombination (2k rec = 4.6 · 109 L mol−1 s−1). In the presence of the Ni(SR)2 complex, coordination of the radical (k coord = 4.4 · 109 L mol−1 s−1) competes with recombination to form a radical complex RS· Ni(SR)2 having an intense absorption band with a maximum at 460 nm (ε = 16 600 L mol−1 cm−1). This species decays in the second-order reaction (2k = 4.6 · 104 L mol−1 s−1). Since the photochromic system returns to the initial state, the reaction of two radical complexes is assumed to produce radical recombination and reduction of the disulfide and Ni(SR)2 complex. Analysis of the kinetic data showed that some RS· radicals decay in the microsecond time interval due to the reaction with the RS· Ni(SR)2 radical complex (k = 3.1 · 109 L mol−1 s−1). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2291–2300, October, 2005.  相似文献   

6.
It was studied the equilibrium adsorption and adsorption kinetics of Cu(II), Cd(II), Pb(II), and Cr(VI) by composite hydroxides formed by Me x O y · nH2O and Me0.4–0.7Al0.6–0.3O y · nH2O, where Me = Zr, Sn and Ti. It was estimated the values of the diffusion coefficients of adsorbed ions Cu(II) and Cr(VI) from kinetic values. It was established that the estimated diffusion coefficients of adsorbed ions Cu(II) are in the range 0.4 × 10−12–2.5 × 10−12 m2/s for individual hydroxides and 1.2 × 10−12–2.8 × 10−12 m2/s for double hydroxides. The obtained values of diffusion coefficients Cr (VI) for double hydroxides are 0.1 × 10−10–0.4 × 10−10 m2/s.  相似文献   

7.
The reaction of the · OH radical with the oxalate ion in an acidic aqueous solution was studied by pulse radiolysis. The rate constant for the reaction of formation of the radical HOOC-COO·(λmax = 250 nm, ɛ = 1800 L mol−1 cm−1) is (5.0±0.5)·107 L mol−1 s−1. In the reaction with the hydrogen ion (k = 1.1·107 L mol−1 s−1), the radical HOOC-COO· is transformed into a nonidentified radical designated arbitrarily as H+(HOOC-COO)· (λmax = 260 nm, ɛ = 4000 L mol−1 cm−1). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1165–1167, June, 2008.  相似文献   

8.
The extraction behavior of Th(IV) from dilute nitric as well as perchloric acid medium using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and its mixture with tri-n-octyl phosphine oxide (TOPO) was investigated. The species of the type Th(X)(PMBP)3·(HPMBP) and Th(X)(PMBP)3·(TOPO) were extracted for the binary and ternary extraction systems, respectively, where X=NO3− or ClO4−. The presence of 1.25·10−5M Th carrier in the aqueous phase resulted in the extracted species of the type of Th(PMBP)4 and Th(PMBP)4·(TOPO), respectively. The extraction constant (logk ex ) for the binary species Th(PMBP)4 was found to be 6.89±0.01 while the overall extraction constant (logK) for the ternary species Th(PMBP)4·(TOPO) was calculated to be 13.17±0.06.  相似文献   

9.
Summary Two novel charge-transfer (CT) heteropoly complexes, (C8H12N2)5H7PMo12O40 (1) and (C8H12N2)3H3-PMo12O40·5H2O (2), prepared by reacting p-Me2NC6H4NH2 with the four-electron heteropoly blue H7PMo12O40·12H2O and heteropoly acid H3PMo12O40· xH2O, respectively, were characterized by elemental analysis, and u.v., i.r., XPS and e.s.r. spectroscopies. A sizable electron-transfer interaction occurs within the product molecules and the heteropoly anions retain their Keggin structure. Their third-order optical non-linearity coefficients were measured using the Z-scan technique at a concentration of 4.68 × 10−6 mol dm−3 for (1) and 2.79 × 10−6 mol dm−3 for (2), with I 0 = 2.38 × 1013 w m−2 and λ = 532nm. The |χ(3)| for (1) is 2.61 × 10−10 esu and |χ(3)| for (2) is 1.05 × 10−10 esu.  相似文献   

10.
The kinetics of the reactions between Fe(phen) 3 2+ [phen = tris–(1,10) phenanthroline] and Co(CN)5X3− (X = Cl, Br or I) have been investigated in aqueous acidic solutions at I = 0.1 mol dm−3 (NaCl/HCl). The reactions were carried out at a fixed acid concentration ([H+] = 0.01 mol dm−3) and the second-order rate constants for the reactions at 25 °C were within the range of (0.151–1.117) dm3 mol−1 s−1. Ion-pair constants K ip for these reactions, taking into consideration the protonation of the cobalt complexes, were 5.19 × 104, 3.00 × 102 and 4.02 × 104 mol−1 dm−3 for X = Cl, Br and I, respectively. Activation parameters measured for these systems were as follows: ΔH* (kJ K−1 mol−1) = 94.3 ± 0.6, 97.3 ± 1.0 and 109.1 ± 0.4; ΔS* (J K−1) = 69.1 ± 1.9, 74.9 ± 3.2 and 112.3 ± 1.3; ΔG* (kJ) = 73.7 ± 0.6, 75.0 ± 1.0 and 75.7 ± 0.4; E a (kJ) = 96.9 ± 0.3, 99.8 ± 0.4, and 122.9 ± 0.3; A (dm3 mol−1 s−1) = (7.079 ± 0.035) × 1016, (1.413 ± 0.011) × 1017, and (9.772 ± 0.027) × 1020 for X = Cl, Br, and I respectively. An outer – sphere mechanism is proposed for all the reactions.  相似文献   

11.
At near neutral pH (approx. 5.5), the OH-adduct of chlorogenic acid (CGA), formed on pulse radiolysis of N2O-saturated aqueous CGA solutions (λ max = 400 and 450 nm) with k = 9 × 109 dm3 mol−1 s−1, rapidly eliminates water (k = 1 × 103 s−1) to give a resonance-stabilized phenoxyl type of radical. Oxygen rapidly adds to the OH-adduct of CGA (pH 5.5) to form a peroxyl type of radical (k = 6 × 107 dm3 mol−1 s−1). At pH 10.5, where both the hydroxyl groups of CGA are deprotonated, the rate of reaction of · OH radicals with CGA was essentially the same as at pH 5.5, although there was a marked shift in the absorption maximum to approx. 500 nm. The CGA phenoxyl radical formed with more specific one-electron oxidants, viz., Br 2 ·− and N 3 · radicals show an absorption maximum at 385 and 500 nm, k ranging from 1–5.5 × 109 dm3 mol−1 s−1. Reactions of other one-electron oxidants, viz., NO 2 · , NO· and CCl3OO· radicals, are also discussed. Repair rates of thymidine, cytidine and guanosine radicals generated pulse radiolytically at pH 9.5 by CGA are in the range of (0.7–3) × 109 dm3 mol−1 s−1.  相似文献   

12.
Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag2(X) m (bip)(NCCH3) n ](X)2−m (X = NO3 , CF3SO3 , ClO4 , BF4 , and PF6 ; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N4 tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH3 versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO3  ≫ CF3SO3  > ClO4  > BF4  ≫ PF6 .  相似文献   

13.
Multilayer films of multiwalled carbon nanotubes (MWNTs) were homogeneously and stably assembled on a glassy carbon (GC) electrode using the layer-by-layer (LBL) method based on electrostatic interaction between MWNTs (negatively charged) and a biopolymer chitosan (CHIT) (positively charged). Scanning electron microscopy (SEM) image of the resulting {CHIT/MWNTs}9 film indicated that the substrate was mostly covered with MWNTs in the form of small bundles or single nanotubes. The multilayer film was used to study the electrocatalytic oxidation of NADH. The assembled {CHIT/MWNTs}9/GC electrode could decrease the oxidation overpotential of NADH by more than 350 mV. The {CHIT/MWNTs}9/GC electrode exhibited a wide linear response range of 8 × 10−7 to 1.6 × 10−3 mol · L−1 with a correlation coefficient of 0.997 for the detection of NADH. The response time and detection limit (S/N = 3) were determined to be 3 s and 0.3 × 10−6 mol · L−1, respectively. Another attractive characteristic was that the method was simple and the assembled {CHIT/MWNTs}9/GC electrode was highly stable.  相似文献   

14.
The reactions between Fe(Phen)32+[phen = tris-(1,10) phenanthroline] and Co(CN)5X3− (X = Cl, Br or I) have been studied in aqueous acidic solutions at 25 °C and ionic strength in the range I = 0.001–0.02 mol dm−3 (NaCl/HCl). Plots of k2 versusI, applying Debye–Huckel Theory, gave the values −1.79 ± 0.18, −1.65 ± 0.18 and 1.81 ± 0.10 as the product of charges (ZAZB) for the reactions of Fe(Phen)32+ with the chloro-, bromo- and iodo- complexes respectively. ZAZB of ≈ −2 suggests that the charge on these CoIII complexes cannot be −3 but is −1. This suggests the possibility of protonation of these CoIII complexes. Protonation was investigated over the range [H+] = 0.0001 −0.06 mol dm−3 and the protonation constants Ka obtained are 1.22 × 103, 7.31 × 103 and 9.90 × 102 dm6 mol−3 for X = Cl, Br and I, respectively.  相似文献   

15.
The formation of neutral Tl2max = 390 nm) and Tl4max = 360 nm) clusters in dilute aqueous solutions of Tl2SO4 containing formate ions was found by pulse radiolysis. The rate constants for the recombination of Tl0 atoms and Tl2 clusters are equal to 1.5·1010 L mol−1 s−1 and 1.0·1010Lmol−1 s−1 (±30%), respectively, and the extinction coefficient of Tl2 at 390 nm is −6.0·103 L mol−1 cm−1 Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2367–2369, December, 1999.  相似文献   

16.
The kinetic data on the molecular oxygen activity of CH3CH·, CH3CF2 · and CF3CHF· radicals are reported. In laboratory, these radicals were generated by pulsed (12 ns) electron beam interaction with the gaseous RHF-O2-CO2 mixtures containing large excess of carbon dioxide (RHF = CH3CH2F, CH3CHF2 or CH2FCF3). The transient product (O3 or RFO2 ·) formation was monitored by the UV absorptions at 250 nm and the rate constants of Reactions (4) and (9) were obtained. The values of k 9 diminished with increasing number of fluorine atoms in RHF molecule. For CH3CH2F and CH3CHF2 the k 9’s were equal to (8.8–10.2)·10−14cm3 ·s−1 and (7.3–8.4)·10−14cm3 ·s−1, respectively, and seem to be determined for the first time. In the case of CH2FCF3 the obtained value of k CF3CHF+O2 = 5.20±0.76·10−14cm3 ·s−1 is much higher than the value published in the literature.4 The other determined rate constant data are comparable to the literature values.  相似文献   

17.
Thermal lens spectrometry was used for the differential kinetic determination of aniline (over the concentration range of 8 × 10−4–3.2 × 10−3 M) and 4-nitroaniline (2 × 10−4–1.6 × 10−3 M) present in combination in a single sample based on the oxidation reaction with periodate ions in an acidic medium (this determination is not possible with the spectrophotometric monitoring of the rate of reaction). The thermal lens procedure (λe = 488.0 nm; 80 mW) was characterized by good performance characteristics in the determination of aniline (c min = 3 × 10−4 M; c d = 8 × 10−4 M) and 4-nitroaniline (c min = 7 × 10−5 M; c d = 2 × 10−4 M), simplicity, and rapidity.  相似文献   

18.
Ab initio quantum chemistry methods were applied to study the bifurcated bent hydrogen bonds Y··· H2CZ (Z = O, S, Se) and Y···H2CZ2 (Z = F, Cl, Br) (Y = Cl, Br) at the MP2/6-311++G(d,p) and MP2/6-311++G(2df,2p) levels. The results show that in each complex there are two equivalent blue-shifted H-bonds Y···H-C, and that the interaction energies and blue shifts are large, the energy of each Y···H-C H-bond is 15–27 kJ/mol, and Δr(CH) = −0.1 − −0.5 pm and Δv(CH) = 30 − 80 cm−1. The natural bond orbital analysis shows that these blue-shifted H-bonds are caused by three factors: large rehybridization; small direct intermolecular hyperconjugation and larger indirect intermolecular hyperconjugation; large decrease of intramolecular hyperconjugation. The topological analysis of electron density shows that in each complex there are three intermolecular critical points: there is one bond critical point between the acceptor atom Y and each hydrogen, and there is a ring critical point inside the tetragon YHCH, so these interactions are exactly H-bonding.  相似文献   

19.
A method with a sensitivity of 2·10−7 to 1·10−10% has been developed for determining Yb, Ho, Dy, Gd, Eu, Sm and La impurities in metallic uranium by means of neutron activation. The method is based on a preliminary chromatographic separation of the total amount of rare earth elements from uranium by passing the solution in sulphuric acid through KU-2 cation exchange resin and eluting the traces of uranium retained by the resin with a solution of ascorbic acid. The rare earth impurities are then eluted from the resin with 4–5N HCl, evaporated, and irradiated for 20 hours with a neutron flux of 1.2·1013 n·cm−2·sec−1. Subsequently the traces of the rare earth elements are co-precipitated with Fe(OH)3, dissolved in concentrated HCl and separated from the iron and other impurities by passing the solution through Dowex 1X8 anion exchange resin in the chloride form. The individual rare earth elements are then separated from each other using KU-2 cation exchange resin and a solution of ammonium α-hydroxyisobutyrate as the eluant.  相似文献   

20.
Two crystal samples, sodium 5-methylisophthalic acid monohydrate (C9H6O4Na2·H2O, s) and sodium isophthalic acid hemihydrate (C8H4O4Na2·1/2H2O, s), were prepared from water solution. Low-temperature heat capacities of the solid samples for sodium 5-methylisophthalic acid monohydrate (C9H6O4Na2·H2O, s) and sodium isophthalic acid hemihydrate (C8H4O4Na2·1/2H2O, s) were measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 379 K. The experimental values of the molar heat capacities in the measured temperature region were fitted to a polynomial equation on molar heat capacities (C p,m) with the reduced temperatures (X), [X = f(T)], by a least-squares method. Thermodynamic functions of the compounds (C9H6O4Na2·H2O, s) and (C8H4O4Na2·1/2H2O, s) were calculated based on the fitted polynomial equation. The constant-volume energies of combustion of the compounds at T = 298.15 K were measured by a precise rotating-bomb combustion calorimeter to be Δc U(C9H6O4Na2·H2O, s) = −15428.49 ± 4.86 J g−1 and Δc U(C8H4O4Na2·1/2H2O, s) = −13484.25 ± 5.56 J g−1. The standard molar enthalpies of formation of the compounds were calculated to be Δ f H m θ (C9H6O4Na2·H2O, s) = −1458.740 ± 1.668 kJ mol−1 and Δ f H m θ (C8H4O4Na2·1/2H2O, s) = −2078.392 ± 1.605 kJ mol−1 in accordance with Hess’ law. The standard molar enthalpies of solution of the compounds, Δ sol H m θ (C9H6O4Na2·H2O, s) and Δ sol H m θ (C8H4O4Na2·1/2H2O, s), have been determined as being −11.917 ± 0.055 and −29.078 ± 0.069 kJ mol−1 by an RD496-2000 type microcalorimeter. In addition, the standard molar enthalpies of hydrated anion of the compounds were determined as being Δ f H m θ (C9H6O4 2−, aq) = −704.227 ± 1.674 kJ mol−1 and Δ f H m θ (C8H4O4Na2 2−, aq) = −1483.955 ± 1.612 kJ mol−1, from the standard molar enthalpies of solution and other auxiliary thermodynamic data through a thermochemical cycle.  相似文献   

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