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1.
Richard Vytlacil 《Monatshefte für Chemie / Chemical Monthly》1980,111(5):1075-1086
In the ternary system silver chloride-lithium chloride-sodium chloride the kinetics of the galvanic deposition of silver on graphite electrodes was investigated as well as its dissolution without current in the molten salt saturated with chlorine gas.In addition the emf-values were measured in the temperature range between 923 K and 1,173 K by means of, the formation cell graphite/Ag(s)/AgCl(l)–LiCl(l)–NaCl(l)/Cl2 graphite From these data the partial molar free excessGibbs energies were calculated. Using the equation for a multicomponent system as suggested byRedlich-Kister
1
G
AgCl
E
values were obtained by a non-linear fitting process, where the fit was performed for all investigated temperatures and over the entire concentration range in the ternary system. With the parameters obtained the partial and integral excess valuesG
i
E
,G
E
,H
i
E
,H
E
,S
i
E
andS
E
were calculated. 相似文献
2.
Stajic M Persky L Hadar Y Friesem D Duletic-Lausevic S Wasser SP Nevo E 《Applied biochemistry and biotechnology》2006,128(1):87-96
Copper (Cu2+) and manganese (Mn2+) ions influenced laccase (Lac) and peroxidase production in Pleurotus eryngii, Pleurotus ostreatus, and Pleurotus pulmonarius. In P. eryngii, the optimum Cu2+ concentration for Lac production was 1 mM and for peroxidases 10mM, and Mn2+ concentration of 5mM led to peaks of Lac and peroxidase activity. In P. ostreatus HAI 493, the highest level of Lac activity was at Cu2+ concentrations of 1 and 10 mM and Mn2+ concentration of 1mM, respectively. The absence of Cu2+ and Mn2+ caused the highest levels of peroxidase production. In P. ostreatus HAI 494, the highest level of Lac activity was at a Cu2+ concentration of 5 mM and at Mn2+ concentration of 1 mM, respectively. High levels of peroxidase activity were found in the medium without and with 1mM Cu2+, and at 1 and 5 mM Mn2+, respectively. In P. pulmonarius, the highest Lac activity was found in the presence of 5 mM Cu2+ and 5 mM Mn2+, respectively. The absence of Cu2+ and Mn2+ as well as their presence at a concentration of 1 mM led to the peaks of peroxidase activities. 相似文献
3.
In the theoretical model it is assumed that a graphite disk electrode is covered by a thin film of solution of decamethylferrocene
(dmfc) and some electrolyte CX in nitrobenzene and immersed in an aqueous solution of the electrolyte MX. Oxidation of dmfc is accompanied by the transfer of anion X
− from water into nitrobenzene since it is also assumed that cations dmfc
+ and C
+ are insoluble in water and cation M
+ is insoluble in nitrobenzene. Kinetic parameters of the electrode reaction can be determined if the total potential difference
across the nitrobenzene/water interface is maintained constant by adding the electrolytes CX and MX in concentrations which are much higher than the initial concentration of dmfc in nitrobenzene. 相似文献
4.
Potentially bi- and tetra-dentateSchiff bases derived from salicylaldehyde react with hydrated uranyl salts to give complexes: UO2H2
LX
2, UO2H2
LX
2 and UO2(HL)2
X
2 [H2
L=N,N-propane-1,3-diylbis(salicylideneimine), H2
L=N,N-ethylenebis(salicylideneimine) and HL=N-phenylsalicylideneimine;X
–=Cl–, Br–, I–, NO3
–, ClO4
–, and NCS–]. Because of marked spectral similrities with the structurally known Ca(H2
L) (NO3)2, theSchiff bases are coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms of the azomethine groups which carry the protons transferred from phenolic groups on coordination. Halide, nitrate, perchlorate and thiocyanate groups are covalently bonded to the uranyl ion, resulting a 6-coordinated uranium ion in the halo and thiocyanato complexes and 8-coordinated in nitrato and perchlorato complexes.
Komplexe von Dioxouranyl(VI) mit zwitterionischen Formen von zwei- und vierzähnigen Schiff-Basen
Zusammenfassung Von Salizylaldehyd abgeleitete zwei- und vierzähnigeSchiff-Basen reagieren mit hydratisierten Uranylsalzen zu Komplexen folgenden Typs: UO2H2 LX 2, UO2H2 LX 2 und UO2(HL)2 X 2 [H2 L=N,N-Propan-1,3-diylbis(salicylidenimin), H2 L=N,N-Ethylen-bis(salicylidenimin) und HL=N-Phenylsalicylidenimin;X –=Cl–, Br–, I–, NO3 –, ClO4 – und NCS–]. Auf Grund eindeutiger spektraler Ähnlichkeiten mit dem bekannten Ca(H2 L) (NO3)2 wird auf Koordination über die negativ geladenen phenolischen Sauerstoffatome (und nicht über die Azomethin-Stickstoffe) geschlossen. Die AnionenX – sind kovalent an das Uranyl-Ion gebunden; damit ergibt sich ein hexakoordiniertes Uranyl-Ion für die Halogen- und Thiocyanat-Komplexe und Oktakoordination für die Nitrat- und Perchlorat-Komplexe.相似文献
5.
Karin Popa Alexandru Cecal Doina Humelnicu Ioan Caraus Camelia L. Draghici 《Central European Journal of Chemistry》2004,2(3):434-445
This study concerns the removal of the 137Cs+ and 60Co2+ β+γ-radioactive ions in Azolla caroliniana Willd. water fern. The living fern and two different types of biosorbent prepared from Azolla caroliniana were tested to remove the above-mentioned radioactive ions from dilute solutions, in the absence and in the presence of the
ionic competition. Effective 137Cs+ and 60Co2+ ions removal from low radioactive wastewaters was demonstrated. The time dependent K
d
(t) values were calculated from the absorption data. These results indicate that removal process achieved equilibrium in about
120 min and that it involves two steps: rapid and slow absorption; the active process (metabolic bioaccumulation on the living
fern) was responsible for above one half of the total removal process. A thin layer radiochromatography study leads to the
conclusion that the biochemical components in which 137Cs+ and 60Co2+ place themselves are of a polysaccharide and lipoid fractions. 相似文献
6.
Maria Cyfert Barbara Latko Maria Wronska 《Monatshefte für Chemie / Chemical Monthly》1980,111(3):619-626
The influence of NaClO4, NaCl and Na2SO4 on the oxidation of Fe(phen)
3
2+
by Ce(IV) was investigated by means of the stopped-flow method. At the concentrations range of NaClO4 and NaCl 0.1–1.0M the rate constant values decrease from 1.03·105 to 0.56·105M–1s–1 and from 1.08·105 to 0.81·105M–1s–1 respectively.In varying concentrations of Na2SO4 solutions (0.05–0.35M) the rate constant values decrease from 1.05·105M–1s–1 to 0.45·105M–1s–1.Taking into account the negative salt effect the mechanism of the reaction progress is proposed. 相似文献
7.
Yue Zhang Natsumi Watanabe Yuuko Miyawaki Yutaka Mune Kenta Fujii Yasuhiro Umebayashi Shin-ichi Ishiguro 《Journal of solution chemistry》2005,34(12):1429-1443
Aprotic N,N-dimethylpropionamide (DMPA) and N,N,N′,N′-tetramethylurea (TMU) are both strong donor solvents and coordinate to metal ions through the carbonyl oxygen atom. These
solvents show a different conformational aspect in the bulk phase, i.e., DMPA exists as either a planar cis or a nonplanar staggered conformer, while TMU exists in a single planar cis conformer. It has been established that the manganese(II) ion is solvated by five molecules in both solvents. Interestingly,
although the planar cis conformer of DMPA is more favorable than the nonplanar staggered one in the bulk phase, the reverse is the case in the coordination
sphere of the metal ion, i.e., a conformational change occurs upon solvation. To reveal the thermodynamic aspect of this conformational change, the complexation
of Mn(II) with bromide ions in DMPA and TMU has been studied by titration calorimetry at 298 K. It was found that the Mn(II)
ion forms mono-, di- and tri-bromo complexes in both solvents, and their formation constants, enthalpies and entropies were
obtained. The Δ H∘1 value for MnBr+ strongly depends on the solvent, i.e., it is positive (19.4 kJ-mol−1) in DMPA and negative (−8.7 kJ-mol−1) in TMU, whereas the Δ H^∘2 and Δ H∘3 values for the stepwise formation of MnBr2 and MnBr3− are both small and negative. The enthalpy of transfer ΔtH∘ from DMPA to TMU, which is evaluated on the basis of the extrathermodynamic TATB assumption, is 25.5 kJ-mol−1 for Mn2+ and −3.6 kJ-mol−1 for MnBr+. These values indicate that the difference between the formation enthalpy of MnBr+ in the two solvents, Δ H^∘1 (DMPA) – Δ H∘1 (TMU), is mainly ascribed to the value of ΔtH∘(Mn2+). It is found that the metal ion is also five-coordinated in the monobromo complex, MnBr(DMPA)4+ . The enthalpy for the conformational change of DMPA from its planar cis to the nonplanar staggered form is evaluated to be −11 and −5.5 kJ-mol−1 for Mn(DMPA)52 + and MnBr(DMPA)4+, respectively. Note that these values are significantly smaller than the corresponding value (5.0 kJ-mol−1) in the bulk phase. We thus conclude that, although steric hindrance among solvent molecules is reduced by replacing one
DMPA of Mn(DMPA)52 + with the relatively small bromide ion, DMPA molecules are still sterically hindered in the MnBr(DMPA)4+ complex. 相似文献
8.
Viscosity measurements were carried out with polyacrylonitrile dissolved in dimethylformamide up to 0.36 g/ml. The temperature range was 20°C to 130°C, the highest shear gradient applied, 5.6·103s–1. The temperature variation of viscosity is reproduced with sufficient accuracy by the equation =k·exp (Q/RT). Bothk andQ increase as concentration increases, and the viscosity increases withc
1.12 toc
6.4 Inverse proportionality appears to exist between concentration and the longest relaxation time. 相似文献
9.
Natarajan Raman Chinnathangavel Thangaraja Samuelraj Johnsonraja 《Central European Journal of Chemistry》2005,3(3):537-555
A novel tetradentate N2O2 type Schiff base, synthesized from 1-phenyl-2,3-dimethyl-4-aminopyrazol-5-one(4-aminoantipyrine) and 3-salicylidene-acetylacetone,
forms stable complexes with transition metal ions such as Cu
II
, Ni
II
, Co
II
and Zn
II
in ethanol. Microanalytical data, magnetic susceptibility, IR, UV-Vis.,1H-NMR, ESR and Mass spectral techniques were used to confirm the structures. Electronic absorption spectra of the complexes
suggest a square-planar geometry around the central metal ion. These complexes show higher conductance values, supporting
their electrolytic nature. The monomeric nature of the complexes was confirmed from their magnetic susceptibility values.
Cyclic voltammogram of the copper(II) and nickel(II) complexes in DMSO solution at 300 K were recorded and the results are
discussed. The X-band ESR spectra of the copper complex were recorded and the molecular orbital coefficient values were calculated
from the spectra. The in vitro antimicrobial activities of the investigated compounds were tested against bacteria such as Klebsiella pneumoniae, Staphylococcus aureus, Bacillus subtilis and Escherichia coli and fungi like Aspergillus niger and Rhizoctonia bataicola. Most of the metal chelates show higher antimicrobial activity for the above microorganisms than that of the free ligand. 相似文献
10.
A simple and effective procedure for the enantioselective synthesis of (R)- and (S)-moprolol was described. The key step was the asymmetric synthesis of enantiopure (R)- and (S)-guaifenesin, which were synthesized from enantioenriched (R)-3-chloro-l,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-Co^Ⅲ complex. The e.e. values of both the optical compounds were above 98%, and the chemical structures of the target compounds were confirmed by ^1H NMR, ^13C NMR, IR, and MS. 相似文献
11.
Kolomnikova G. D. Petrovskii P. V. Sorokin P. V. Dolgushin F. M. Yanovsky A. I. Chizhevsky I. T. 《Russian Chemical Bulletin》2001,50(4):706-715
The reaction of OsCl2(PPh3)3 with [nido-7-R1-8-R2-C2B9H10]K+ produced a series of new exo-nido-osmacarborane complexes exo-nido-5,6,10-[Cl(Ph3P)2Os]-5,6,10-(-H)3-10-H-7-R1-8-R2-7,8-C2B9H6 (1: R1 = R2 = H; 2: R1 = R2 = Me; 3: R1 = R2 = PhCH2; 4: R1 + R2 = 1,2-C6H4(CH2)2; 5: R1 = H, R2 = Me) in which the osmium-containing group is linked to the nido-carborane ligand through three two-electron three-center bonds. Compounds 1—5 are formed as mixtures of symmetric (a) and asymmetric (b) isomers; pure symmetric isomers 2a and 4a were isolated by fractional crystallization, and the mixture of isomers 3a, was quantitatively separated into individual compounds 3a and 3b by column chromatography on silica gel. Detailed analysis of the 31P{1H}, 1H, 11B NMR spectra of 1a,b—5a,b and 2D 1H-1H{11B} and 11B{1H}-11B{1H} NMR spectra of 3a and 3b was performed. The structures of isomers 2a and 4a were confirmed by an X-ray diffraction study. According to the NMR and X-ray diffraction data, the isomerism of exo-nido-complexes 1a,b—5a,b is actually the cis—trans-isomerism of ligand arrangement in the octahedral coordination of the Os atom. 相似文献
12.
The results of kinetic and equilibrium experiments with the set of reaction of proton abstraction from 4-nitrophenyl[bis(ethylsulphonyl)]methane
in acetonitrile are reported. Two strong organic bases are used: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene
(MTBD).
The rates of proton transfer reaction have been measured by T-jump method in the presence of perchlorate of the appropriate
base as a common cation BH+ and supporting electrolyte-tetrabutylammonium perchlorate (TBAP) in the temperature range between 20–40°C are: k
H
=1.32×107−2.00×107 and 2.82×107−4.84×107 dm 3mol−1s−1 for MTBD and TBD respectively. The enthalpies of activation ΔH
MTBD
≠
=13.5 and ΔH
TBD
≠
=18.1 kJmol−1. The entropies of activation are negative: ΔS
MTBD
≠
=−62.3 and ΔS
TBD
≠
=−40.3 Jmol−1K−1.
The change of the absorbance of the anion of 4-nitrophenyl[bis9ethylsulphonyl)]methane at the temperature 25°C in the presence
of common cation BH+ gives the equilibrium constants K=705 and 906 M−1 for MTBD and TBD respectively.
Kinetic and equilibrium results are discussed. The possible mechanism of proton transfer reaction between 4-nitrophenyl[bis(ethylsulphonyl)]methane
and cyclic organic bases: MTBD and TBD in acetonitrile is proposed. 相似文献
13.
Stepovik L. P. Martinova I. M. Dodonov V. A. Cherkasov V. K. 《Russian Chemical Bulletin》2002,51(4):638-644
Tri-tert-butoxyaluminum reacts with tert-butyl hydroperoxide to produce di-tert-butoxy-tert-butyl alumotrioxide, which decomposes heterolytically to form singlet dioxygen and homolytically with the O—O bond cleavage. The ButOO·, (ButO)2AlOO·, ButO·, and (ButO)2AlO· radicals were identified by ESR using spin traps. These findings confirm the formation of aluminum-containing trioxide. The above radicals initiate alkylarene oxidation by the tri-tert-butoxyaluminum—tert-butyl hydroperoxide system. The carbon-centered and alkylperoxy radicals originated from the oxidized substrates were identified. 相似文献
14.
Enn Otsa L. S. Kudrjawzewa O. G. Eisen E. M. Piotrowskaja 《Monatshefte für Chemie / Chemical Monthly》1980,111(3):607-617
The vapour-liquid equilibrium data obtained from isobarict-x-measurements have been used for calculation of the group UNIFAC parameters and excess free enthalpyG
E
of binary mixturesn-alkanes with isomericn-alkynes. The UNIFAC model gives satisfactory predictions for the systems studied. The temperature dependence ofG
E
was estimated on the basis of the heats of mixing measured earlier. The influence of the position of triple bond in the molecules ofn-alkynes on the excess thermodynamic functions is considered. 相似文献
15.
S. A. Shevelev I. L. Dalinger T. K. Shkineva B. I. Ugrak V. I. Gulevskaya M. I. Kanishchev 《Russian Chemical Bulletin》1993,42(6):1063-1068
A method of synthesizing nitro derivatives of lH,4H-pyrazolo[4,3-c]pyrazole is developed, and some of its transformations are studied. 3-Methyl-6-nitro-, 3-carboxy(methoxy-carbonyl, carbamoyl)-6-nitro-, 3-amino-6-nitro-, 3-nitro-, 3,6-dinitro-, 1,4-diacetonyl-3,6-dinitro-, and lH,4H-3-aminopyrazolo[4,3-c]pyrazoles were obtained from 1H,4H-3 -methylpyrazolo[4,3-c]pyrazole. Unsubstituted 1H,4H-pyrazolo[4,3-c]pyrazole, the first member of this series, was obtained for the first time. The compounds prepared were characterized by1H,13C,14N, and15N NMR spectroscopy. NH-Acidity and basicity of the series of pyrazolo[4,3-c]pyrazoles synthesized is studied and the effect of the fused pyrazole ring on these properties is examined.Deceased March 18, 1989.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1108–1113, June, 1993. 相似文献
16.
I. Capek 《Central European Journal of Chemistry》2003,1(3):291-304
The kinetics of free-radical copolymerization and terpolymerization of acrylamide (AAm), N, N′-methylenebis(acrylamide) (MBA) and methacrylic acid (MA) in the inverse water/monomer/cyclohexane/Tween 85 miniemulsion was
investigated. Polymerizable sterically-stable miniemulsions were formulated in cyclohexane as a continuous medium. Polymerizations
are very fast and reach the final conversion within several minutes. The dependence of the polymerization rate vs. conversion
is described by a curve with two nonstationary rate intervals. The maximum rate of polymerization slightly increases with
increasing concentration of crosslinking monomer (MBA) and strongly decreases by the addition of MA. The rate of polymerization
is inversely proportional to the 0.9
th
and 1.8
th
power of the particle concentration without and with MA, respectively. The number of polymer particles is inversely proportional
to the 0.18
th
and 0.13
th
power of MBA concentration. The kinetic and colloidal parameters of the miniemulsion polymerization are discussed in terms
of microemulsion polymerization model. 相似文献
17.
Alfred Vendl 《Monatshefte für Chemie / Chemical Monthly》1979,110(1):103-108
The crystal structure of NbMoN1–x
has been determined from X-ray powder patterns. It is isotypic with the formerly described1,2 complex nitrides NbCrN and Ta1–x
Cr1+x
N. The tetragonal unit cell contains 6 atoms and belongs to the space groupP4/nmm-D
4h
7. The lattice parameters are:a=3,095 Å,c=7,799 Å. The structure is characterized by relatively close packed double layers of Nb-atoms and Mo-atoms parallel to the base plane. The nitrogen atoms are within the octahedral interstitial sites. 相似文献
18.
Axel-Rüdiger Schulze Hanskarl Müller-Buschbaum 《Monatshefte für Chemie / Chemical Monthly》1981,112(2):149-156
The hitherto unknown compound Ca3Ga4O9 was prepared and investigated by X-ray single crystal methods. Ca3Ga4O9 has orthorhombic symmetry:a=1435.8;b=1682.5;c=532.1 pm; space group C
2v
11
–Cmm2,Z=6. The tetrahedra network (circles of 4 and 5 GaO4-tetrahedra) and the surrounding of Ca2+ are described and discussed with respect to other oxogallates. 相似文献
19.
On the electrochemical reduction of some Cr(III) complexes inDMSO investigated by cyclic voltammetry
The compounds investigated were: [Cr(en)3]3+, [Cr(ur)6]3+, [Cr(DMSO)6]3+, [Cr(dien)2]3+, [Cr(en)2(acac)]2+, [Cr(en) (acac)2]+ and Cr(acac)3.A distinctly different behaviour is caused by the introduction of one or moreacac ligands into the molecule. The first step is much more cathodic and quite irreversible, while it is reversible or quasi reversible for the first group of ions. This is due to a -type interaction between theacac ligand and the central ion. This interaction is responsible for a third peak occurring for the second group of compounds and may be attributed to the reduction of the Cr(I) ion.Some correlations were found e.g. between the extinction of thed-d band of the first group of ions and the potential of the first peak, and the number ofacac groups introduced in the second group of compounds and the shift of the potential of the first peak.The determined electrochemical data are tabulated.
Untersuchungen zur elektrochemischen Reduktion einiger Cr(III)-Komplexe in DMSO mittels zyklischer Voltammetrie
Zusammenfassung Die elektrochemischen Daten einer Reihe von Cr(III)-Komplexen miten-, ur-, DMSO-, dien- undacac-Liganden werden präsentiert und einige Möglichkeiten der Korrelation der physikalischen Eigenschaften der Komplexe werden aufgezeigt.Die erste Stufe bei der Einführung vonacac-Liganden ist auf Grund einer -Wechselwirkung zwischen Ligand und Zentralion irreversibel.相似文献
20.
N,N-dimethyl-3-oxa-glutaramic acid was purified and characterized by 1H-NMR, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis. The thermal decomposition of the title compound
was studied by means of thermogravimetry differential thermogravimetry (TG-DTG) and FT-IR. The kinetic parameters of its second-stage
decomposition reaction were calculated and the decomposition mechanism was discussed. The kinetic model function in a differential
form, apparent activation energy and pre-exponential constant of the reaction are 3/2 [(1−α)1/3−1]−1, 203.75 kJ·mol−1 and 1017.95s−1, respectively. The values of ΔS
≠, ΔH
≠ and ΔG
≠ of the reaction are 94.28 J·mol−1·K−1, 203.75 kJ·mol−1 and 155.75 kJ·mol−1, respectively.
Supported by the National Natural Science Foundation of China (Grant No. 20106009) 相似文献