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1.
Solubility of Oxygen in Some 1-1, 2-1, 1-2, and 2-2 Electrolytes as a Function of Concentration at 25°C 总被引:1,自引:0,他引:1
The solubility of oxygen has been measured in a number of electrolytes [(LiCl, KCl, RbCl, CsCl, NaF, NaBr, NaI, NaNO3, KBr, KI, KNO3, CaCl2, SrCl2, BaCl2, Li2SO4, K2SO4, Mn(NO3)3)] as a function of concentration at 25°C. The solubilities, mol (kg-H2O)–1, have been fitted to a function of the molality m (standard deviation < 3mol-kg–1)
where A and B are adjustable parameters and the activity coefficient of oxygen )O2) = [O2]0/[O2]. The limiting salting coefficient, k
S = (ln / m)m=0 = A, was determined for all salts. The salting coefficients for the chlorides and sodium salts showed a near linear correlation with the crystal molar volume V
cryst = 2.52 r
3. The salting coefficients determined from the Scaled Particle Theory were in reasonable agreement with the measured values. The activity coefficients of oxygen in the solutions have been interpreted using the Pitzer equation
where
is a parameter that accounts for the interaction of O2 with cations (c) and anions (a) with molalities m
a and m
c, and
accounts for interactions for O2 with the cation and anion pair (c-a). The
and
coefficients determined for the most of the ions are in reasonable agreement with the tabulations of Clegg and Brimblecombe. The values of
for most of the ions are a linear function of the electrostriction molar volume (Velect = V0 – V
cryst). 相似文献
2.
The enthalpies and entropies of evaporation of Al(CH3)3–Sn(CH3)4and Ga(CH3)3–Sn(CH3)4solutions were determined. It was established that solvates are formed in these systems and that the dissociation energies of specific interactions in them change in the following order:
(10.3) >
>
>
(4.08 kJ mol–1),
(6.52) >
(5.14) >
>
(4.08 kJ mol–1). 相似文献
3.
The oxidation of H2NOH is first-order both in [NH3OH+] and [AuCl4
–]. The rate is increased by the increase in [Cl–] and decreased with increase in [H+]. The stoichiometry ratio, [NH3OH+]/[AuCl4
–], is 1. The mechanism consists of the following reactions.
The rate law deduced from the reactions (i)–(iv) is given by Equation (v) considering that [H+] K
a.
The reaction (iii) is a combination of the following reactions:
The activation parameters for the reactions (ii) and (iii) are consistent with an outer-sphere electron transfer mechanism. 相似文献
4.
Summary The oxidation of H2O2 by [W(CN)8]3– has been studied in aqueous media between pH 7.87 and 12.10 using both conventional and stopped-flow spectrophotometry. The reaction proceeds without generation of free radicals. The experimental overall rate law,
, strongly suggests two types of mechanisms. The first pathway, characterized by the pH-dependent rate constant k
s, given by
, involves the formation of [W(CN)8· H2O2]3–, [W(CN)8· H2O2·W(CN)8]6– and [W(CN)8· HO]3– intermediates in rapid pre-equilibria steps, and is followed by a one-electron transfer step involving [W(CN)8·HO]3– (k
a) and its conjugate base [W(CN)8·O]4– (k
b). At 25 °C, I = 0.20 m (NaCl), the rate constant
with H
a
=40±6kJmol–1 and S
a
=–151±22JK–1mol–1; the rate constant
with H
b
=36±1kJmol–1 and S
b
=–136±2JK–1mol–1 at 25 °C, I = 0.20 m (NaCl); the acid dissociation constant of [W(CN)8·HO]3–, K
5
=(5.9±1.7)×10–10
m, with
and
is the first acid dissociation constant of H2O2. The second pathway, with rate constant, k
f, involves the formation of [W(CN)8· HO2]4– and is followed by a formal two-electron redox process with [W(CN)8]3–. The pH-dependent rate constant, k
f, is given by
. The rate constant k
7
=23±6m
–1
s
–1 with
and
at 25°C, I = 0.20 m (NaCl). 相似文献
5.
Polosukhin A. I. Bondarev O. G. Lyubimov S. E. Shiryaev A. A. Petrovskii P. V. Lysenko K. A. Gavrilov K. N. 《Russian Journal of Coordination Chemistry》2001,27(8):591-597
Phosphorylation of (S)-prolinol with P(NEt2)3was used to synthesize aminophosphite (2R,5S)-
, which was reacted with the corresponding amino alcohols to afford (2S,5R)-
(Va) and (2S,5R)-
(Vb). Reaction of Vawith [Rh(CO)2Cl]2(P/Rh = 1) yields the mononuclear chelate [Rh(CO)(P^N)Cl] (VIIa), while the analogous reaction with Vbresults in a mixture of products with cis- and trans-orientation of the coordinated phosphorus and nitrogen atoms. Spectral characteristics of the products of coordination of ligands Vaand Vbwere compared with those for the binuclear reference complex [Rh(CO)(L)Cl]2(VIII), where L is P-monodentate ligand (2S,5R)-
(VI). The ligands and complexes were studied by IR, NMR, 31P and 13C spectroscopy, mass spectrometry, and elemental analysis methods. X-ray diffraction analysis of crystals VIIIwas performed. 相似文献
6.
The mechanism of the Co(II) catalytic electroreduction of water insoluble CoR2 salt in the presence of cysteine was developed. CoR2 = cobalt(II) cyclohexylbutyrate is the component of a carbon paste electrode. Electrode surface consecutive reactions are:
(a) fast (equilibrium) reaction of the complex formation, (b) rate-determining reversible reaction of the promoting process of CoR(Ac+) complex formation, (c) rate-determining irreversible reaction of the electroactive complex formation with ligand-induced adsorption, and (d) fast irreversible reaction of the electroreduction. Reactions (a,b) connected with CoR2 dissolution and reactions (c,d) connected with CoR2 electroreduction are catalyzed by . Regeneration of (reactions “b,d”) and accumulation of atomic Co(0) (reaction “d”) take place. Experimental data [Sugawara et al., Bioelectrochem
Bioenergetics 26:469, 1991]: i
a vs E (i
a is anodic peak, E is cathodic accumulation potential), i
a vs , and i
a vs pH have been quantitatively explained. 相似文献
7.
Isothermal compressibilities T and isobaric thermal expansion coefficients p have been determined for mixtures of ethylbenzene+n-nonane, +n-decane, and +n-dodecane at 25 and 45°C in the whole range of composition. The excess functions
and
have been obtained at each measured mole fraction. The first one
is zero for ethylbenzene +n-nonane, positive for ethylbenzene +n-decane, and +n-dodecane and increases with chain length n of the n-alkane. The
function is positive for the three studied systems and nearly constant with n. Both mixing functions increase slightly with temperature. From this measurement and supplementary literature data of molar heat capacities at constant pressure C
P
, the isentropic compressibilities S, the molar heat capacities at constant volume C
V
and the corresponding mixing functions have been calculated at 25°C. Furthermore, the pressure dependence of excess enthalpy H
B
,
at zero pressure and at 25°C has been obtained from our experimental results of
and experimental literature values for excess volume V
E
. 相似文献
8.
François Quentel Valentin Mirčeski Maurice L’Her 《Journal of Solid State Electrochemistry》2008,12(1):31-39
Thermodynamics and kinetics of hydrophilic ion transfers across water|n-octanol (W|OCT) interface have been electrochemically studied by means of novel three-phase and thin-film electrodes. Three-phase
electrodes used for thermodynamics measurements comprise edge plane pyrolytic graphite, the surface of which was partly modified
with an ultrathin film of OCT, containing hydrophobic lutetium bis(tetra-tert-butylphthalocyaninato) (Lu[tBu4Pc]2) as a redox probe. The transfers of anions and cations from W to OCT were electrochemically driven by reversible redox transformations
of Lu[tBu4Pc]2 to chemically stable lipophilic monovalent cation and anion , respectively. Upon reduction of Lu[tBu4Pc]2, the transfers of alkali metal cations from W to OCT have been studied for the first time, enabling estimation of their Gibbs
transfer energies. For kinetic measurements, a thin-film electrode configuration has been used, consisting of the same electrode
covered completely with a thin layer of OCT that contained the redox probe and a suitable electrolyte. Combining the fast
and sensitive square-wave voltammetry with thin-film electrodes, the kinetics of , , and Cl− transfers have been estimated.
Dedicated to Professor Dr. Yakov I. Tur’yan on the occasion of his 85th birthday. 相似文献
9.
Reena Singh Atanu Banerjee Yee Gordon Kajal Krishna Rajak 《Transition Metal Chemistry》2009,34(6):689-694
Abstract The title complexes and have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with H2L1 and H2L2, respectively, in acetonitrile solution. Here, [L1]2− and [L2]2− are the deprotonated forms of N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine and N,N-bis(2-hydroxybenzyl)-2-picolylamine, respectively. The crystal structures of and were determined by x-ray crystallography. In , each cobalt atom has distorted trigonal bipyramid geometry, while in , each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic
interaction in . The magnetic characterization for is in agreement with the presence of Co(II) and Co(III) centers.
Graphical Abstract The title complexes and have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with dianionic N2O2 coordinating ligands. In complex 1, each cobalt atom has distorted trigonal bipyramid geometry, while in complex 2, each
cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic
interaction in complex 1. The magnetic characterization for complex 2 is in agreement with the presence of Co(II) and Co(III)
centers.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
10.
By analyzing the topological structures of the three types of icosahedral fullerenes: (1)
, (2)
and (3)
k,\;h,k = 1,2,...} \right)$$
" align="middle" border="0">
, we have obtained theoretically the 13C NMR spectra with natural abundance for 13C of all the icosahedral (Ih and I) fullerenes. 相似文献
11.
Reinaldo F. Teófilo Helder J. Ceragioli Alfredo C. Peterlevitz Leonardo M. Da Silva Flavio S. Damos Márcia M. C. Ferreira Vitor Baranauskas Lauro T. Kubota 《Journal of Solid State Electrochemistry》2007,11(10):1449-1457
The electrochemical properties of boron-doped diamond (BDD) polycrystalline films grown on tungsten wire substrates using
ethanol as a precursor are described. The results obtained show that the use of ethanol improves the electrochemistry properties
of “as-grown” BDD, as it minimizes the graphitic phase upon the surface of BDD, during the growth process. The BDD electrodes
were characterized by Raman spectroscopy, scanning electronic microscopy, cyclic voltammetry (CV), and electrochemical impedance
spectroscopy (EIS). The boron-doping levels of the films were estimated to be ∼1020 B/cm3. The electrochemical behavior was evaluated using the and redox couples and dopamine. Apparent heterogeneous electro-transfer rate constants were determined for these redox systems using the CV and EIS techniques. values in the range of 0.01–0.1 cm s−1 were observed for the and redox couples, while in the special case of dopamine, a lower value of 10−5 cm s−1 was found. The obtained results showed that the use of CH3CH2OH (ethanol) as a carbon source constitutes a promising alternative for manufacturing BDD electrodes for electroanalytical
applications. 相似文献
12.
The solubility of rhodochrosite (MnCO3) at 25°C under constant carbon dioxide partial pressure p(CO2) was determined in NaCl solutions as a function of ionic strength I. The dissolution of MnCO3(s) for the reaction
has been determined as a function of pH. From these values, we have determined the equilibrium constant for the stoichiometric solubility of MnCO3(s) in NaCl solutions
These values have been fitted to the equation
with a standard error of = 0.1 with Iand concentrations in molalities. The extrapolated value of log K
o
sp(–10.3) in water is in good agreement with literature data (–10.1 to 10.8) determined in solutions of different composition and ionic strength. The measured values of the activity coefficient, T(Mn2+) and T(CO3
2–), have been used to estimate the stability constant for the formation of the MnCO3ion pair, K
*(MnCO3
0). The value of K
0(MnCO3
0) calculated from the values of K
*(MnCO3) by the Pitzer equation ( = 0.1) in this study (4.8 ± 0.1) is in reasonable agreement with literature data. 相似文献
13.
Tomohiro Nuida Toshiya Hozumi Hiroko Tokoro Kazuhito Hashimoto Shin-ichi Ohkoshi 《Journal of Solid State Electrochemistry》2007,11(6):763-772
This article describes novel optical functionalities such as photomagnetic effects and magnetization-induced second harmonic
generation (MSHG) in several cyano-bridged metal assemblies. Single crystal- and film-types of a cyano-bridged Cu–Mo bimetallic
assembly, , were electrochemically prepared. When this compound was irradiated with light, spontaneous magnetization with a Curie temperature
(T
C) of 23 K was observed. Electrochemically prepared FeII[CrIII(CN)6]2/3·5H2O thin film, which was a ferromagnet with T
C=21 K, showed photoreduced magnetization. This photomagnetism is due to the change of ferromagnetic coupling between FeII and CrIII. MSHG was observed in CsICoII[CrIII(CN)6]·0.5H2O. This -type Prussian blue analog-based magnet is proven to be a piezoelectric ferromagnet, i.e., condensed matter with both piezoelectric
and ferromagnetism. This MSHG is due to the coupling between a piezoelectric structure of and ferromagnetism with a T
C of 46 K.
相似文献
Shin-ichi OhkoshiEmail: |
14.
The equilibrium constant for the hydrolytic disproportionation of I2
has been determined at 25°C and at ionic strength 0.2 M(NaClO4) in buffered solution. The reaction was followed in the pH range where the equilibrium concentration of I2, I–, and IO3
–are commensurable, i.e., the fast equilibrium
is also established. The equilibrium concentrations of I2and I3
–were determined spectrophotometrically, and the concentrations of all the other species participating in process (1) were calculated from the stoichiometric constraints. The constants determined are \log K_1 = -47.61\pm 0.07 and \log K_2 = 2.86 \pm 0.01. 相似文献
15.
The reaction of ethyleneimine with sulfenyl chlorides RSCl at –10 C in the presence of a hydrogen chloride acceptor (triethylamine) leads to the formation of N-organylthioaziridines
. Compounds with R=n-C5H11, C6H5, o-O2NC6H4 and C6H6CH2 have been obtained by this method.
and
. have been synthesized analogously.The properties and IR spectra of these compounds have been studied. The action of methyl iodide on N-phenylthioaziridine leads to disproportionation of the molecule with the formation of diphenyl disulfide, -iodoethyltrimethylammonium iodide, and free iodine.For communication VI, see [I]. 相似文献
16.
Indium tin-oxide (ITO) and polycrystalline boron-doped diamond (BDD) have been examined in detail using the scanning electrochemical microscopy technique in feedback mode. For the interrogation of electrodes made from these materials, the choice of mediator has been varied. Using ferrocene methanol (FcMeOH), and approach curve experiments have been performed, and for purposes of comparison, calculations of the apparent heterogeneous electron transfer rates (k
app) have been made using these data. In general, it would appear that values of k
app are affected mainly by the position of the mediator reversible potential relative to the relevant semiconductor band edge (associated with majority carriers). For both the ITO (n type) and BDD (p type) electrodes, charge transfer is impeded and values are very low when using FcMeOH and as mediators, and the use of
results in the largest value of k
app. With ITO, the surface is chemically homogeneous and no variation is observed for any given mediator. Data is also presented where the potential of the ITO electrode is fixed using a ratio of the mediators
and
In stark contrast, the BDD electrode is quite the opposite and a range of k
app values are observed for all mediators depending on the position on the surface. Both electrode surfaces are very flat and very smooth, and hence, for BDD, variations in feedback current imply a variation in the electrochemical activity. A comparison of the feedback current where the substrate is biased and unbiased shows a surprising degree of proportionality.Dedicated to Alan, a good friend and colleague on his 60th birthday. 相似文献
17.
Luminescence Behavior of Polynuclear Alkynylcopper(I) Phosphines 总被引:1,自引:0,他引:1
A series of soluble trinuclear and tetranuclear copper(I) complexes containing 3-l acetylides
, and
have been synthesized and shown to exhibit rich photoluminescent behavior at room temperature. The electrochemistry of the trinuclear Cu(I) acetylide complexes and the excited-state redox properties of
have been investigated. The X-ray crystal structures of
and
have been determined. 相似文献
18.
Dissociation Constants for Citric Acid in NaCl and KCl Solutions and their Mixtures at 25 °C 总被引:1,自引:0,他引:1
The constants for the dissociation of citric acid (H3C) have been determined from potentiometric titrations in aqueous NaCl and KCl solutions and their mixtures as a function of ionic strength (0.05–4.5 mol-dm–3) at 25 °C. The stoichiometric dissociation constants (Ki*)
were used to determine Pitzer parameters for citric acid (H3C), and the anions, H2C–, HC2–, and C3–. The thermodynamic constants (Ki) needed for these calculations were taken from the work of R. G. Bates and G. D. Pinching (J. Amer. Chem. Soc. 71, 1274; 1949) to fit to the equations (T/K):
The values of Pitzer interaction parameters for Na+ and K+ with H3C, H2C–, HC2–, and C3– have been determined from the measured pK values. These parameters represent the values of pK1*, pK2*, and pK3*, respectively, with standard errors of = 0.003–0.006, 0.015–0.016, and 0.019–0.023 for the first, second, and third dissociation constants. A simple mixing of the pK* values for the pure salts in dilute solutions yield values for the mixtures that are in good agreement with the measured values. The full Pitzer equations are necessary to estimate the values of pKi* in the mixtures at high ionic strengths. The interaction parameters found for the mixtures are Na-K – H2C = – 0.00823 ± 0.0009; Na-K – HC = – 0.0233 ± 0.0009, and Na-K – C = 0.0299 ± 0.0055 with standard errors of (pK1) = 0.011, (pK2) = 0.011, and (pK3) = 0.055. 相似文献
19.
Anna Rita Campanelli Fabio Ramondo Aldo Domenicano István Hargittai 《Structural chemistry》1999,10(1):29-40
The molecular structure and conformation of p-bis(trimethylsilyl)benzene have been investigated by gas-phase electron diffraction, ab initio MO calculations at the HF/6-31G*, MP2(f.c.)/6-31G*, and B3LYP/6-31G* levels, and MM3 molecular mechanics calculations. The calculations indicate the syn- and anti-coplanar conformations, with two
bonds in the plane of the benzene ring, to be energy minima. The perpendicular conformations, with two
bonds in a plane orthogonal to the ring plane, are transition states. The two coplanar conformers have nearly the same energy with a low interconversion barrier, 0.3–0.5 kJ mol–1. The calculated lengths of the
and
bonds differ by only a few thousandths of an angstrom, in agreement with electron diffraction results from molecules containing either
or
bonds. The geometrical distortion of the benzene ring in p-bis(trimethylsilyl)-benzene may be described by superimposing independent distortions from each of the two SiMe3 groups. The electron diffraction intensities from a previous study (Rozsondai, B.; Zelei, B.; Hargittai, I. J. Mol. Struct.
1982, 95, 187) have been reanalyzed, imposing constraints from the theoretical calculations, and using a model based on a 1:1 mixture of the two coplanar conformers. The effective torsion angles of the SiMe3 groups may indicate nearly free rotation. Important geometrical parameters from the present electron diffraction analysis are
, and
. While the mean bond lengths are virtually the same from the previous and present analyses, the new ipso angle is in better agreement with the MO calculations [HF, 116.9° MP2(f.c.), 117.1° B3LYP, 116.9°]. 相似文献
20.
Friedrich Hammerschmidt Prof. Dr. Erich Zbiral 《Monatshefte für Chemie / Chemical Monthly》1977,108(6):1253-1263
2-Acylcyclopropane carboxylic acids (1) are degraded by aHunsdiecker reaction using red HgO/Br2 to mixtures oftrans- andcis-2-bromo-cyclopropyl alkanones, the former being the major component. The starting materials may be easily prepared by reaction of stabilised S-ylides
with ,-unsaturated oxo compounds or -acylvinyltriphenylphosphonium bromides. 相似文献