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1.
M. Jiménez-Reyes M. Solache-Ríos A. Rojas-Hernández 《Journal of solution chemistry》2006,35(2):201-214
The specific ion interaction theory (SIT) was applied to the first hydrolysis constants of Eu(III) and solubility product
of Eu(OH)3 in aqueous 2, 3 and 4 mol⋅dm−3 NaClO4 at 303.0 K, under CO2-free conditions. Diagrams of pEuaq versus pCH were constructed from solubilities obtained by a radiometric method, the solubility product log10 Ksp, Eu(OH)3I {Eu(OH)3(s)
Euaq3++ 3OHaq− } values were calculated from these diagrams and the results obtained are log10 Ksp,Eu(OH)3I = − 22.65 ± 0.29, −23.32 ± 0.33 and −23.70 ± 0.35 for ionic strengths of 2, 3 and 4 mol⋅dm−3 NaClO4, respectively. First hydrolysis constants {Euaq3++H2O
Eu(OH)(aq)2++H+ } were also determined in these media by pH titration and the values found are log10βEu,HI = − 8.19 ± 0.15, −7.90 ± 0.7 and −7.61 ± 0.01 for ionic strengths of 2, 3, and 4 mol⋅dm−3 NaClO4, respectively. Total solubilities were estimated taking into account the formation of both Eu3+ and Eu(OH)2+ (7.7 < pCH < 9) and the values found are: 1.4 × 10−6 mol⋅dm−3, 1.2 × 10−6 mol⋅dm−3 and 1.3 × 10−6 mol⋅dm−3, for ionic strengths of 2, 3 and 4 mol⋅dm−3 NaClO4, respectively. The limiting values at zero ionic strength were extrapolated by means of the SIT from the experimental results
of the present research together with some other published values. The results obtained are log10 Ksp, Eu(OH)3o = − 23.94 ± 0.51 (1.96 SD) and log10βEu,H0 = − 7.49 ± 0.15 (1.96 SD). 相似文献
2.
The quantitative study of the equilibrium Pu4++Cl−⇋Pu3++1/2 Cl2 in LiCl−KCl (70–30% mol) at 455, 500, 550 and 600°C by visible and near I.R. absorption spectrophotometry allows the calculation
of the reaction's equilibrium constant, the mean thermodynamic data ΔH=27±14 kJ·mol−1 and ΔS=37±17 J·mol−1·K−1 and the standard potential of the couple
.
相似文献
3.
The stoichiometric solubility constant of eitelite (NaMg
0.5
CO
3
+2H+ ⇄ Na++0.5Mg
2+
+CO
2
(g)+H
2
O, log*K
pso
I
=14.67±0.03 was determined at I=3 m (mol kg−1) (NaClO
4
) and 25°C. The stability of magnesium (hydrogen-)carbonato complexes in this ionic medium was explicitely taken into account.
Consequently, trace activity coefficients of free ionic species, calculated from the Pitzer model with ion-interaction parameters
from the literature, were sufficient for an evaluation of the thermodynamic solubility constants and Gibbs energies of formation
for eitelite (−1039.88±0.60), magnesite (−1033.60±0.40), hydromagnesite (−1174.30±0.50), nesquehonite (−1724.67±0.40), and
brucite (−835.90±0.80 kJ-mol
−1
). The increasing solubilities of nesquehonite and eitelite at higher sodium carbonate molalities were explained by invoking
a magnesium dicarbonato complex (Mg2++2CO
3
2−
⇄ Mg(CO3)
2
2−
, log βz = 3.90 ± 0.08). A set of ion-interaction parameters was obtained from solubility and dissociation constants for carbonic
acid in 1 to 3.5 m NaClO
4
media
which reproduce these constants to 0.02 units in log K. The following Pitzer parameters are consistent with the previously
studied formation of magnesium (hydrogen-)carbonato complexes in 3m NaClO
4
. The model and Gibbs functions of solid phases derived here reproduce original solubility data (−log [H+], [Mg
2+
]
tot
) measured in perchlorate medium within experimental uncertainty.
Presented at the XXII International Conference on Solution Chemistry, July 14–19, 1991, Linz, Austria. 相似文献
4.
Stefan Perişanu Iulia Contineanu Mircea D. Banciu Hui Zhao Nigam Rath James Chickos 《Structural chemistry》2006,17(6):639-648
Condensed and gas phase enthalpies of formation of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1, (−199.1 ± 16.4), (−70.5 ± 20.5) kJ mol−1, respectively) and 3,4,6,7-dibenzobicyclo[3.2.1]nona-3,6-dien-2-one (2, (−79.7 ± 22.9), (20.1 ± 23.1) kJ mol−1) are reported. Sublimation enthalpies at T=298.15 K for these compounds were evaluated by combining the fusion enthalpies at T = 298.15 K (1, (12.5 ± 1.8); 2, (5.3 ± 1.7) kJ mol−1) adjusted from DSC measurements at the melting temperature (1, (T
fus, 357.7 K, 16.9 ± 1.3 kJ mol−1)); 2, (T
fus, 383.3 K, 10.9 ± 0.1) kJ mol−1) with the vaporization enthalpies at T = 298.15 K (1, (116.1 ± 12.1); 2, (94.5 ± 2.2) kJ mol−1) measured by correlation-gas chromatography. The vaporization enthalpies of benzoin ((98.5 ± 12.5) kJ mol−1) and 7-heptadecanone ((94.5 ± 1.8) kJ mol−1) at T = 298.15 K and the fusion enthalpy of phenyl salicylate (T
fus, 312.7 K, 18.4 ± 0.5) kJ mol−1) were also determined for the correlations. The crystal structure of 1 was determined by X-ray crystallography. Compound
1 exists entirely in the enol form and resembles the crystal structure found for benzoylacetone. 相似文献
5.
6.
Oxidation of 3-(4-methoxyphenoxy)-1,2-propanediol (MPPD) by bis(hydrogenperiodato) argentate(III) complex anion, [Ag(HIO6)2]5− has been studied in aqueous alkaline medium by use of conventional spectrophotometry. The major oxidation product of MPPD
has been identified as 3-(4-methoxyphenoxy)-2-ketone-1-propanol by mass spectrometry. The reaction shows overall second-order
kinetics, being first-order in both [Ag(III)] and [MPPD]. The effects of [OH−] and periodate concentration on the observed second-order rate constants k′ have been analyzed, and accordingly an empirical expression has been deduced:
where [IO4
−]tot denotes the total concentration of periodate and k
a = (0.19 ± 0.04) M−1 s−1, k
b = (10.5 ± 0.3) M−2 s−1, and K
1 = (5.0 ± 0.8) × 10−4 M at 25.0 °C and ionic strength of 0.30 M. Activation parameters associated with k
a and k
b have been calculated. A mechanism is proposed, involving two pre-equilibria, leading to formation of a periodato–Ag(III)–MPPD
complex. In the subsequent rate-determining steps, this complex undergoes inner-sphere electron-transfer from the coordinated
MPPD molecule to the metal center by two paths: one path is independent of OH−, while the other is facilitated by a hydroxide ion. 相似文献
7.
Stability constants of the form F
β
1(M)=[MF2+][M3+]−1[F−]−1 (where [MF2+] represents the concentration of a yttrium or a rare earth element (YREE) complex, [M3+] is the free YREE ion concentration, and [F−] is the free fluoride ion concentration) were determined by direct potentiometry in NaNO3 and NaCl solutions. The patterns of log10
F
β
1(M) in NaNO3 and NaCl solutions very closely resemble stability constant patterns obtained previously in NaClO4. For a given YREE, stability constants obtained in NaClO4 were similar to, but consistently larger than F
β
1(M) values obtained in NaNO3 which, in turn, were larger than formation constants obtained in NaCl. Stability constants for formation of nitrate and chloride
complexes (
and Cl
β
1(M)=[MCl2+][M3+]−1[Cl−]−1) derived from F
β
1(M) data exhibited ionic strength dependencies generally similar to those of F
β
1(M). However, in contrast to the somewhat complex pattern obtained for F
β
1(M) across the fifteen member YREE series, no patterns were observed for nitrate and chloride complexation constants: neither
nor Cl
β
1(M) showed discernable variations across the suite of YREEs. Nitrate and chloride formation constants at 25 °C and zero ionic
strength were estimated as log10
and log10
Cl
β
1o(M)=0.71±0.05. Although these constants are identical within experimental uncertainty, the distinct ionic strength dependencies
of
and Cl
β
1(M) produced larger differences in the two stability constants with increasing ionic strength whereby Cl
β
1(M) was uniformly larger than
. 相似文献
8.
Kinetics of aqua ligand substitution from cis-[Ru(bpy)2(H2O)2]2+ by three vicinal dioximes, namely dimethylglyoxime (L1H), 1,2-cyclohexane dionedioxime (L2H) and α-furil dioxime (L3H) have been studied spectrophotometrically in the 45–60 °C temperature range. The rate constants increase with increasing
dioxime concentration and approach a limiting condition. We propose the following rate law for the reaction in the 3.5–5.5
pH range: where k
2 is the interchange rate constant from outer sphere to inner sphere complex and K
E is the outer sphere association equilibrium constant. Activation parameters were calculated from the Eyring plots for all
three systems: ΔH
≠ = 59.2 ± 8.8, 63.1 ± 6.8 and 69.7 ± 8.5 kJ mol−1, ΔS
≠ = −122 ± 27, −117 ± 21 and −99 ± 26 J K−1 mol−1 for L1H, L2H and L3H, respectively. An associative interchange mechanism is proposed for the substitution process. Thermodynamic parameters calculated
from the temperature dependence of the outer sphere association equilibrium constants give negative ΔG
0 values for all the systems studied at all the temperatures (ΔH
0 = 30.05 ± 2.5, 18.9 ± 1.1 and 11.8 ± 0.2 kJ mol−1; ΔS
0 = 123 ± 8, 94 ± 3 and 74 ± 1 J K−1 mol−1 for L1H, L2H and L3H, respectively), which also support our proposition. 相似文献
9.
Complex formation constants were determined potentiometrically (by a ISE-H+, glass electrode) in the systems, M2+ – Lz – H+ [M2+ = (C2H5)2Sn2+, Lz = malonate, glycinate and ethylenediamine] at t = 25 ∘C and 0.1 mol-L−1≤ I/ ≤ 1 mol-L−1 in NaClaq (0.1 mol-L−1 ≤ I ≤ 0.75 mol-L−1 for the ethylenediamine system). Thermodynamic values of formation constants, at infinite dilution, are [± 95% confidence
interval, Tβpqr refer to the equilibrium, pM2+ + qLz + rH+ = MpLqHr(2+z+r)]: for malonate, log10 Tβ110 = (5.47 ± 0.10); for glycinate, log10 Tβ110 = (9.54 ± 0.08), log10 Tβ111 = (12.97 ± 0.10); and for ethylenediamine, log10 Tβ110 = (10.47 ± 0.10), log10 Tβ120 = (16.17 ± 0.12) and log10 Tβ111 = (15.46 ± 0.10). The dependence on ionic strength of the formation constants was modeled by a simple Debye–Hückel type equation
and by the SIT approach. By analyzing the stability of the species in the three different systems we found a simple additivity
rule that can be expressed by the relationship: log10 K = 6.46 nN + 3.96 nO − 0.60 (nN2+ nO2), with a mean deviation, ε(log10 K) = 0.15 (K = equilibrium constant for the interaction of the organometal cation with the unprotonated or protonated ligand, nN = number of amino groups and nO = number of carboxylic groups of the ligand(s) involved in the formation reaction of complex species). 相似文献
10.
Reactor neutron activation analysis of antimony, indium and cadmium in high-purity tin is interfered with by nuclear reactions
on the tin matrix. For a number of interfering reactions the cross-sections were determined. The following results were obtained:122Sn(n,γ)123mSn:σth=0.145 barn, I=0.79 barn;122Sn(n,γ)113Sn:σth=0.52, I=25.4 barn;112Sn(n, 2n)111Sn:
microbarn;118Sn(n, α)115Cd:
microbarn; and114Sn(n, p)114m1In:
microbarn. 相似文献
11.
Lyudmila A. Belyakova Oleksandra M. Shvets Diana Yu. Lyashenko 《Central European Journal of Chemistry》2008,6(4):581-591
The present work investigates the adsorptive interactions of Hg(II) ions in aqueous medium with hydroxylated silica, aminopropylsilica
and silica chemically modified by β-cyclodextrin. Batch adsorption studies were carried out with various agitation times and
mercury(II) concentrations. The maximum adsorption was observed within 15–30 min of agitation. The kinetics of the interactions,
tested with the model of Lagergren for pseudo-first and pseudo-second order equations, showed better agreement with first
order kinetics (k1 = 3.4 ± 0.2 to 5.9 ± 0.3 min−1). The adsorption data gave good fits with Langmuir isotherms. The results have shown that β-cyclodextrin-containing adsorbent
has the largest adsorption specificity to Hg(II): K
L
= 4125 ± 205 mmol−1. “β-cyclodextrin-NO3-” inclusion complexes with ratio 1: 1 and super molecules with composition C42H70O35 ⊎ 3 Hg(NO3)2 are formed on the surface of β-cyclodextrin-containing silica.
相似文献
12.
Effect of pH and ionic strength on the interaction of humic acid with aluminium oxide 总被引:4,自引:0,他引:4
E. Tombácz Á. Dobos M. Szekeres H. D. Narres E. Klumpp I. Dékány 《Colloid and polymer science》2000,278(4):337-345
The effect of pH and neutral electrolyte on the interaction between humic acid/humate and γ-AlOOH (boehmite) was investigated.
The quantitative characterization of surface charging for both partners was performed by means of potentiometric acid–base
titration. The intrinsic equilibrium constants for surface charge formation were logK
a,1
int=6.7±0.2 and logK
a,2
int = 10.6±0.2 and the point of zero charge was 8.7±0.1 for aluminium oxide. The pH-dependent solubility and the speciation of
dissolved aluminium was calculated (MINTEQA2). The fitted (FITEQL) pK values for dissociation of acidic groups of humic acid were pK
1 = 3.7±0.1 and pK
2 = 6.6±0.1 and the total acidity was 4.56 mmol g−1. The pH range for the adsorption study was limited to between pH 5 and 10, where the amount of the aluminium species in the
aqueous phase is negligible (less than 10−5 mol dm−3) and the complicating side equilibria can be neglected. Adsorption isotherms were determined at pH ∼ 5.5, ∼8.5 and ∼9.5,
where the surface of adsorbent is positive, neutral and negative, respectively, and at 0.001, 0.1, 0.25 and 0.50 mol dm−3 NaNO3. The isotherms are of the Langmuir type, except that measured at pH ∼ 5.5 in the presence of 0.25 and 0.5 mol dm−3 salt. The interaction between humic acid/humate and aluminium oxide is mainly a ligand-exchange reaction with humic macroions
with changing conformation under the influence of the charged interface. With increasing ionic strength the surface complexation
takes place with more and more compressed humic macroions. The contribution of Coulombic interaction of oppositely charged
partners is significant at acidic pH. We suppose heterocoagulation of humic acid and aluminium oxide particles at pH ∼ 5.5
and higher salt content to explain the unusual increase in the apparent amount of humic acid adsorbed.
Received: 20 July 1999 /Accepted in revised form: 20 October 1999 相似文献
13.
I. V. Mironov 《Russian Journal of Inorganic Chemistry》2008,53(4):655-659
The transformations of Au(OH) 4 ? in aqueous solutions (T = 20°C, I = 1) containing NH3 and NH 4 + (pH 8.1–8.5) were studied. The most pronounced changes in the system occur in the range 0 > log [NH 4 + ] > ?2.0 (c Au = (1?10) × 10?4 mol/L, the monitoring time was about two weeks). When log [NH 4 + ] > 0, Au(NH3) 4 3+ dominates together with the amido form Au(NH3)3NH 2 2+ ; when log [NH 4 + ] < ?2.0, no changes in the spectra are observed, probably, because of the very low rate of the processes. As c Au increases in the indicated range, the polymerization rate grows. The equilibrium constant for Au(NH3)3OH2+ + NH3 = Au(NH3) 4 3+ + OH is log $ K_{4 OH, NH_3 } The transformations of Au(OH)4− in aqueous solutions (T = 20°C, I = 1) containing NH3 and NH4+ (pH 8.1–8.5) were studied. The most pronounced changes in the system occur in the range 0 > log [NH4+] > −2.0 (c
Au = (1−10) × 10−4 mol/L, the monitoring time was about two weeks). When log [NH4+] > 0, Au(NH3)43+ dominates together with the amido form Au(NH3)3NH22+; when log [NH4+] < −2.0, no changes in the spectra are observed, probably, because of the very low rate of the processes. As c
Au increases in the indicated range, the polymerization rate grows. The equilibrium constant for Au(NH3)3OH2+ + NH3 = Au(NH3)43+ + OH is log = −4.2 ± 0.3. This constant was used together with other constants, taking into account possible ligand effects, to estimate
the formation constant of Au(NH3)43+: logβ4 = 47 ± 1, E
3/0 = 0.64 ± 0.02 V, log = −8.5 ± 1 (substitution of 4 NH3 for 4 OH− in Au(OH)4−), log = 17.5 ± 1 (substitution of 4NH3 for 4Cl− in AuCl4−).
Original Russian Text ? I.V. Mironov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 4, pp. 711–715. 相似文献
14.
The relative thermodynamic stabilities of 2,5-dihydrofuran (1) and 2,3-dihydrofuran (2), and of 3,4-dihydro-6H-pyran (3) and 3,4-dihydro-2H-pyran (4), were determined at several temperatures by base-catalyzed equilibration in DMSO solution. For 1 → 2, = –15.4±0.1 kJ mol−1, =–12.6±0.5 kJ mol−1, and =9.5±1.3 J K−1 mol−1 at 298.15 K. The second-law reaction enthalpy agrees with literature data based on calorimetric enthalpies of hydrogenation of the isomeric forms in hexane. For 3 → 4, =–19.3±0.2 kJ mol−1, = –18.9±1.1 kJ mol−1 and =1.1±3.0 J K−1 mol−1 at 298.15 K: the experimental reaction enthalpy is in marked disagreement with literature data based on estimation. On the other hand, both of the experimental reaction enthalpies of the present study are in good agreement with DFT calculations using the B3LYP functional and 6-311+G(2d,p) basis set. 相似文献
15.
A procedure to estimate the uncertainty of measurement applied to the fluoride determination of waters and wastewaters matrices
by selective electrode potentiometry was implemented based on Eurachem Guide. The major sources of uncertainty were identified
as the calibration standard solutions, fluoride concentration obtained by potential interpolation of the regression line and
the precision. However the relative uncertainties depend on the anion concentration levels. The methodology proposed was presented
to two fluoride concentration levels that are in the range of surface water samples (C
sample=1.12 mgF l−1) and of wastewater matrices (C
sample=101.4 mgF l−1). The expanded uncertainties calculated were 0.40 and 9.1 mg l−1 for low and high concentration levels, respectively, using the reproducibility uncertainty as precision evaluation. The relative
expanded uncertainty was around ±10% for the highest concentration, which can be considered acceptable for the ion selective
electrode potenciometric methods and ±36% for the lowest concentrations. In this case the sample fluoride content is very
close to the limit of quantification which has a relative uncertainty of about ±30%. If the repeatability was used in spite
of duplicate analysis the same conclusions were obtained (C
sample=1.12 ± 0.39 mgF l−1 and C
sample=101.4 ± 7.0 mgF l−1).
Although the calculated expanded uncertainties and consequently the combined uncertainty, do not vary significantly in the
cases where it was used the repeatability or reproducibility for evaluating the precision, each relative variances uncertainty
contributions do. When the repeatability is used to determine the combined uncertainty, the CSS and uncertainties contributions are the most dominant ones. However, if reproducibility is used, relative uncertainty variance
contributions are distributed among CSS, C
F, and precision. In both cases, the contribution increases and r
CSS contribution decreases with the increasing of the concentration level. The precision variance contribution is only significant
in the case where the reproducibility is used, and increases with the increasing of the concentration level. The uncertainty
in the result calculated using the proposed methodology (C
sample ± U
sample = 2.17 ± 0.42 mgF l−1) is in satisfactory agreement with the estimated expanded uncertainty obtained using the relative reproducibility standard
deviation obtained in interlaboratory studies (). 相似文献
16.
A. Simonits S. Jovanović F. De Corte L. Moens J. Hoste 《Journal of Radioanalytical and Nuclear Chemistry》1984,82(1):169-179
When making use of some single comparator or absolute standardization methods in reactor neutron and in epicadmium neutron activation analysis, the knowledge of the effective resonance energy (
) is essential to correct for the effect of the nonideal epithermal flux distribution on the analysis result.
can be calculated from neutron resonance data, but when these are incomplete, not accurate or even not known at all, experimental determination should be considered. Such a method, providing both
and the resonance integral to 2200 ms–1 cross-section ratio (QO), is described in this paper. Results are given for 11 isotopes. 相似文献
17.
The rate of reaction of NO
2
−
ion with various FeIII porphyrins in the presence of PPh3 is shown to depend on the redox potential of the FeIII center. There is a linear relationship between the ease of reduction of the FeIII to FeII and the kinetics for the formation of the FeII porphyrin nitrosyl adduct, with concomitant oxidation of PPh3 to PPh3O. Cyclic voltammograms show reversible one-electron reductions that can be ascribed to the FeIII/FeII couple ranging from E1/2 = −343 to −145 mV (versus Ag/AgCl). The order of increasing half-wave reduction potentials for the FeIII/FeII porphyrin redox centers studied is octaethylporphyrin > etioporphyrin I > deuteroporphyrin IX dimethyl ester > protoporphyrin
IX dimethyl ester > α,β,γ,δ-tetraphenylporphyrin. This sequence of redox potentials complements the pseudo first-order kinetics
(
to
m s
−1) for the oxidation of PPh3 and subsequent FeII porphyrin nitrosyl adduct formation. The rates of reaction of biomimetic FeIII porphyrins with NO
2
−
ion demonstrate how metal center redox properties are influenced by the surrounding ligand. In this paper we have elucidated
a possible mechanistic control for the rate of this reaction. 相似文献
18.
The gold(III) 1,3-diaminopropane complex [Au(1,3-pn)(1,3-pn-H)]Cl2 has been synthesized. Its dissociation constant has been determined: Au(1,3-pn)23+ = Au(1,3-pn-H)2+ + H+, logK
a1 = −7.03 ± 0.05 (I = 0.1 mol/L NaClO4). Considerable spectral changes are observed for strong alkali solutions (pH 11–14) containing the monoamido forms of the
gold(III) ethylenediamine, 1,3-diaminopropane, and diethylenetriamine complexes (Au(en)(en-H)2+, Au(1,3-pn)(1,3-pn-H)2+, Au(dien-H)OH+). These changes are attributed to the formation of the diamido species Au(en-H)2+, Au(1,3-pn-H)2+, and Au(dien-2H)OH0. The dissociation constants of the monoamido complexes have been determined: Au(en)(en-H)2+ (logK
a2 = −10.9 ± 0.1 at I = 0.001–0.01 mol/L NaCl); Au(1,3-pn)(1,3-pn-H)2+ (logK
a2 = −11.3 ± 0.1 at I = 0.1 mol/L NaCl); Au(dien-H)OH+ (logK
a2 = −12.4 ± 0.1 at I = 0.1 mol/L NaCl). 相似文献
19.
Non-perovskite SrFeCo0.5O
x
(SFC2) was found to have high electronic and ionic conductivities as well as structural stability. At 800°C in air, total
and ionic conductivities of 17 and 7 S·cm−1 were measured, respectively; the ionic transference number was calculated to be ≈0.4. This material is unique because of
its high electronic conductivity and comparable electronic and ionic transference numbers. X-ray diffraction analysis showed
that air-sintered SFC2 consists of three phase components, ≈75 wt% , ≈20 wt% perovskite , and ≈5 wt% rock salt CoO. Argon-annealed SFC2 contains brownmillerite Sr2(Fe1−x
Co
x
)2O5 and rock salt CoO. Dense SFC2 membranes were able to withstand large pO2 gradients and retain mechanical strength. A 2.9-mm-thick disk membrane was tested in a gas-tight electrochemical cell at
900°C; an oxygen permeation flux rate ≈2.5 cm3(STP)·cm−2·min−1 was measured. A dense thin-wall tubular membrane of 0.75-mm thickness was tested in a methane conversion reactor for over
1,000 h. At 950°C, the oxygen permeation flux rate was ≈10 cm3(STP)·cm−2·min−1 when the SFC2 thin-wall membrane was exposed with one side to air and the other side to 80% methane balanced with inert gas.
Results from these two independent experiments agreed well. The SFC2 material is a good candidate as dense ceramic membranes
for oxygen separation from air or for use in methane conversion reactors. 相似文献
20.
J. M. Santana-Casiano M. González-Dávila F. J. Millero 《Journal of solution chemistry》2008,37(6):749-762
The stability constants for the hydrolysis of Cu(II) and formation of chloride complexes in NaClO4 solution, at 25 °C, have been examined using the Pitzer equations. The calculated activity coefficients of CuOH+, Cu(OH)2, Cu2(OH)3+, Cu2(OH)22+, CuCl+ and CuCl2 have been used to determine the Pitzer parameter (β
i
(0), β
i
(1), and C
i
) for these complexes. These parameters yield values for the hydrolysis constants (log 10
β
1*, log 10
β
2*, log 10
β
2,1* and log 10
β
2,2*) and the formation of the chloride complexes (log 10
β
CuCl* and
that agree with the experimental measurements, respectively to ±0.01,±0.02,±0.03,±0.06,±0.03 and ±0.07.
The stability constants for the hydrolysis and chloride complexes of Cu(II) were found to be related to those of other divalent
metals over a wide range of ionic strength. This has allowed us to use the calculated Pitzer parameters for copper complexes
to model the stability constants and activity coefficients of hydroxide and chloride complexes of other divalent metals. The
applicability of the Pitzer Cu(II) model to the ionic strength dependence of hydrolysis of zinc and cadmium is presented.
The resulting thermodynamic hydroxide and chloride constants for zinc are
and
. For cadmium the thermodynamic hydrolysis constants are
and
. The Cu(II) model allows one to determine the stability of other divalent metal complexes over a wide range of concentration
when little experimental data are available. More reliable stepwise stability constants for divalent metals are needed to
test the linearity found for the chloro complexes. 相似文献