LJUNGSKILE: a program for assessing uncertainties in speciation calculations

Speciation calculations are often the base upon which further and more important conclusions are drawn, e.g., solubilities and sorption estimates used for retention of hazardous materials. Since speciation calculations are based on experimentally determined stability constants of the relevant chemical reactions, the measurement and experimental uncertainty in these constants will affect the reliability of the simulation output. The present knowledge of the thermodynamic data relevant for predicting the behaviour of a complex chemical system is quite heterogeneous. In order to predict the impact of these uncertainties on the reliability of a simulation output requires sophisticated modelling codes. In this paper, we will present a computer program, LJUNGSKILE, which utilises the thermodynamic equilibrium code PHREEQC to statistically calculate uncertainties in speciation based on uncertainties in stability constants. A short example is included.     

Uncertainties in Solubility Calculations

Summary.  When considering the possible migration of hazardous elements in groundwater, one has to take into account several phenomena, e.g. solubility, ion exchange, adsorption, matrix diffusion, and transport paths. Here, we focus upon the solubility which in turn depends on several more or less uncertain chemical properties. Uncertainties in the data during laboratory experiments aiming at measurements of thermodynamic constants may cause uncertainties in the amount of some species of several tenths of the relative mass fraction. The thermodynamic data may then be used for solubility calculations under different conditions and water compositions. Clearly, there are several uncertainties associated with solubility calculations in the rock-water system. First, there is the effect of uncertainties in thermodynamic data such as stability and solubility constants, and also enthalpies of reaction if the water is not at room temperature. Furthermore, there are the rock-water interactions which will change the water composition as different minerals come in contact with the water flowing through a system of fractures. Studies in mineralogy to an accuracy good enough for modeling of water evolution are difficult to perform, and therefore the mineral composition of the rock and thus the water composition should be treated as parameters subjected to uncertainties. In addition, there are also conceptual uncertainties with respect to input data. The calculation of a solubility should be an easy task for every chemist, but in fact results differing by orders of magnitude are found even when the modelers have used the same computer program and the same data. In this paper, uncertainties associated with solubility calculations are discussed. The results are exemplified on the calculated solubilities of some actinides in groundwater from crystalline rock. Received August 21, 2000. Accepted (revised) May 18, 2001     

Solubilities of metal hydroxides

The solubilities of freshly precipitated and aged hydroxides of 21 metals have been calculated. The initial data set used for calculations comprised the stability constants and solubility products of hydroxides. The compositions and pHs of saturated solutions and the solubilities of hydroxides are dictated by the polarizing ability of charged metal atoms. The results of solubility calculations are in satisfactory agreement with experimental values.     

ANiN(A=Li,Na,Mg,Ca)的结构、热力学、弹性和电子性质的第一性原理研究

三元过渡金属氮化物ANiN(A=Li,Na,Mg,Ca)是潜在的可充放电池的电极材料.物理性质,比如热稳定性、电子能隙以及弹性稳定性等,对于这些材料的电池应用都是非常重要的.本文使用第一原理方法,对比研究了 ANiN这些材料的结构、动力学、弹性和电子结构性质.对状态方程和声子谱的计算被用来确定体系的稳定结构.对最稳定结...     

Uncertainty analysis of correlated stability constants

Every attempt of using a computer to model reality has two main uncertainties: the conceptual uncertainty and the data uncertainty. The conceptual uncertainty deals with the choice of model selected for the simulation and the data uncertainty is about the precision and accuracy of the input data. They are often determined experimentally and may thus be encumbered by a number of uncertainties. Normally when treating uncertainties in input data these data are treated as independent variables. However, since many of these parameters are determined together they are actually correlated. This paper focuses on chemical stability constants, a most important parameter for chemical calculations based on speciation. Commonly in the literature they are at best given with an uncertainty interval. We propose to also give the covariance matrix thus giving the opportunity to really assess correlations. In addition we discuss the effect of these correlations on speciations.     

Precise polarographic determination of the stability constants of cadmium and lead with oxalate and sulphate

Precise polarographic determinations of the stability constants of some complexes of lead and cadmium with oxalate and sulphate were made using differential-pulse polarography, normal- pulse polarography and direct-current polarography at three different concentrations of the metal ions in the range 1 × 10^?4 to 9 × 10^?8 M. The stability constants, evaluated with the DeFord-Hume procedure, at the different metal ion concentrations and using the different techniques are in good agreement with each other and with literature values. In the calculations corrections were made for changes in liquid-junction potentials and the effect of alterations in the diffusion coefficient of the reactant was also considered for diffusion towards a spherical electrode. For metal ion concentrations above approximately 10^?6 M the precision of the determinations of the half-wave potentials and of the calculations of the stability constants approaches that commonly obtained in potentiometric measurements on similar systems.     

An evaluation of voltammetric titration procedures for the determination of trace metal complexation in natural waters by use of computers simulation

The impact of random analytical errors on the determination of metal complexation parameters of natural waters by metal titration procedures based on cathodic stripping (CSV) or anodic stripping (ASV) voltammetry is investigated by means of computer simulation. The results indicate that random analytical errors are of overriding importance in establishing the range of ligand concentrations and conditional stability constants that can be accurately determined by these techniques. Simulations incorporating realistic estimates of random analytical error show that only stability constants lying within a relatively narrow range, typically three orders of magnitude, can be determined accurately by the ASV procedure. The CSV procedure suffers from the same limitations, but is potentially more flexible in that the available detection window can be moved (but not widened) by adjustments to the method. Both techniques are capable of accurately determining ligand concentrations provided that the corresponding stability constant, K′, is greater than a threshold value which corresponds to the lower end of the available detection window for the stability constant. Realistically attainable improvements in analytical precision did not greatly improve the performance of either technique. Two graphical treatments for the evaluation of metal complexation parameters from titration data are compared: the Scatchard and Van den Berg/Ruzic plots. Simulations indicate that at least for the single-ligand model of complexation, the Van den Berg/Ruzic method is superior. The importance of the simulation results with respect to determining metal complexation parameters in natural waters is discussed. This study illustrates the value of computer simulation when complex, time-consuming analytical techniques are applied and the need for rigorous analysis of errors in producing data of environmental relevance.     

Highly Stable Lithium Metal Anode Interface via Molecular Layer Deposition Zircone Coatings for Long Life Next‐Generation Battery Systems

Herein, molecular layer deposition is used to form a nanoscale “zircone” protective layer on Li metal to achieve stable and long life Li metal anodes. The zircone‐coated Li metal shows enhanced air stability, electrochemical performance and high rate capability in symmetrical cell testing. Moreover, as a proof of concept, the protected Li anode is used in a next‐generation Li‐O₂ battery system and is shown to extend the lifetime by over 10‐fold compared to the batteries with untreated Li metal. Furthermore, in‐situ synchrotron X‐ray absorption spectroscopy is used for the first time to study an artificial SEI on Li metal, revealing the electrochemical stability and lithiation of the zircone film. This work exemplifies significant progress towards the development and understanding of MLD thin films for high performance next‐generation batteries.     

Potentialities of thermal lens spectrometry in studying peculiarities of reactions at the trace level

It was shown that thermal lensing can be used for studying peculiarities of the reactions at the nanogram reactant concentrations. Examples of determining molar absorptivities, dissociation constants of acids, cumulative and stepwise stability constants of complexes, characteristic rate constants, solubility constants, and other parameters using the data of thermal-lens experiments are presented. In a number of cases, taking into account reaction conditions at the nanogram level improves the performance characteristics of the determination.     

Enhanced Active Sites and Stability in Nano-MOFs for Electrochemical Energy Storage through Dual Regulation by Tannic Acid

The limited active sites and poor acid-alkaline solution stability of metal–organic frameworks (MOFs), significantly limit their wider application. In this study, the acid property of tannic acid (TA) was used as an etchant to etch the surface-active sites. Subsequently, the further chelation of the protonated TA with the exposed metal active site can effectively protect the metal ions. Meanwhile, the TA provided a large amount of phenolic hydroxyl groups, which can greatly improve the stability of imidazolate-coordinated MOFs. The electrochemical test results indicated that the MOFs composite materials synthesized using this scheme had high specific capacitance and stability. And the mechanism of its electrochemical reaction process was explored through in situ X-ray diffraction (XRD) and theoretical calculations. In addition, the same treatment was carried out through a series of carboxyl-coordinated MOFs, which further confirmed the principle of this scheme to obtain a higher active site and stability. This paper explains the mechanism of functionalization of nano-MOFs by polyphenolic compounds, providing new ideas for the research of nano-MOFs.     

混合金属氧化物阳极在海水中的电化学性能

采用热分解方法制备钛基混合金属氧化物阳极 ,用扫描电镜对阳极涂层显微形貌进行了分析 ,并通过实海模拟试验考察了混合金属氧化物阳极在海水阴极保护系统中的使用性能 .SEM分析结果表明 ,混合金属氧化物阳极涂层呈多孔多裂纹的显微结构 ,与其它阳极材料相比 ,此种阳极具有更大的活性表面积 .电化学试验结果表明 ,混合金属氧化物阳极在海水中具有良好的电化学稳定性和电化学活性 ;此外 ,混合金属氧化物阳极在海水中的消耗率很低 ,属于不溶性的阳极材料 ,作为外加电流阴极保护的辅助阳极具有广泛的应用前景     

Stability and Structure of Activated Macrocycles. Ligands with Biological Applications

Single p-toluic acid pendant groups were attached to 1,4,7,10,13-pentaazacyclopentadecane (15aneN5) and 1,4,8,11-tetraazacyclotetradecane (cyclam) to prepare bifunctional reagents for radiolabeling monoclonal antibodies with (64,67)Cu. The ligands are 1,4,7,10,13-pentaazacyclopentadecane-1-(alpha-1,4-toluic acid) (PCBA) and 1,4,8,11-tetraazacyclotetradecane-1-(alpha-1,4-toluic acid) (CPTA). For the parent macrocycles and their pendant arm derivatives, the 1:1 Cu(2+) complexes dissociate only below pH 2. At pH 0.0 and 25 degrees C the CPTA-Cu complex has a half-life toward complete dissociation of 24 days. A new approach was developed for the estimation of the Cu(2+) stability constant for the kinetically robust CPTA. All other formation constants were determined at 25.0 degrees C with batch spectrophotometric techniques. Potentiometric titrations were used to determine the protonation constants of the macrocyclic ligands as well as of the metal chelates. The protonation constants, stability constants, and pM's are discussed in terms of both molecular mechanics calculations and the ligands' potential applicability as copper(II) radiopharmaceuticals.     

Catalysis of radiationless transitions in anthracene by coordination compounds of cobalt

Complexes of Co²⁺ with EDTA, cyclohexanediamine tetraacetate (CHDTA), and diethylenetriamine pentaacetate(DTPA)have been used with the triplet state of anthracene at 25 C in ethylene glycol. The deactivation rate increases with the concentration of the addend. Kinetic spectrophotometry has been used to determine the rate constants for deactivation; the results are compared with those for analogous compounds of nickel [1]. The deactivation rate is dependent on the central atom and on the addend. It is supposed that deactivation occurs by formation of a charge-transfer complex between the molecule in the triplet state and the metal ion by interaction between vacant or partly filled d-orbitals on the metal ion and a molecular orbital of the anthracene. The nominal stability constants of the cobalt complexes are deduced from the deactivation rate constants.We are indebted to L. I. Budarin for valuable advice and for discussions.     

Supramolecular interaction of transition metal complexes with albumins and DNA: Spectroscopic methods of estimation of binding parameters

Binding parameters of metal complexes with albumins and DNA since the middle of 1990s are considered and summarized. The most widespread spectroscopic methods of estimation of binding parameters are discussed – direct fluorescent methods, indirect fluorescent methods (by fluorescence quenching parameters), and ways of estimation of binding constants by other optical spectroscopic methods. The methods and approaches to calculations used for the determination of binding constants are discussed. The data on the already found binding constants and kinetic parameters is systematized.     

Complexes between divalent metals and carboxylic acids: Semiempirical study

The possibility to predict the stability constants of the complexes of magnesium, zinc, cadmium, and lead cations with anions of different carboxylic acids by PM3 calculations was investigated. Linear correlation between calculated complex-formation reaction enthalpies and experimentally measured stability constants were obtained for complexes of each metal, while the overall correlation was not satisfactory. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 62: 653–658, 1997     

A DFT and TD-DFT approach to the understanding of statistical kinetics in substitution reactions of M3Q4 (M = Mo, W; Q = S, Se) cuboidal clusters

For many years it has been known that the nine water molecules in [M(3)Q(4)(H(2)O)(9)](4+) cuboidal clusters (M = Mo, W; Q = S, Se) can be replaced by entering ligands, such as chloride or thiocyanate, and kinetic studies carried out mainly on the substitution of the first water molecule at each metal centre reveal that the reaction at the three metal centres occurs with statistical kinetics; that is, a single exponential with a rate constant corresponding to the reaction at the third centre is observed instead of the expected three-exponential kinetic trace. Such simplification of the kinetic equations requires the simultaneous fulfilment of two conditions: first that the three consecutive rate constants are in statistical ratio, and second that the metal centres behave as independent chromophores. The validity of those simplifications has been checked for the case of the reaction of [Mo(3)S(4)(H(2)O)(9)](4+) with Cl(-) by using DFT and TD-DFT theoretical calculations. The results of those calculations are in agreement with the available experimental information, which indicates that the H(2)O ligands trans to the μ-S undergo substitution much faster than those trans to the μ(3)-S. Moreover, the energy barriers for the substitution of the first water molecule at the three metal centres are close to each other, the differences being compatible with the small changes in the numerical values of the rate constants required for observation of statistical kinetics. TD-DFT calculations lead to calculated electronic spectra, which are in reasonable agreement with those experimentally measured, but the calculations do not indicate that the three metal centres behave as independent chromophores, although the mathematical conditions required for simplification of the kinetic traces to a single exponential are reasonably well fulfilled at certain wavelengths. A re-examination of the kinetics of the reaction by using global fitting procedures yields results, which are compatible with statistical kinetics, although an alternative interpretation in which substitution only occurs at a single metal centre under reversible conditions is also possible.     

Nanometer-size cluster formation in alkali-metal-doped fullerene layers

Kinetic Monte Carlo methods have been used to simulate structural transformations in fullerene layers during electrochemical intercalation with alkali-metal ions (A). Special attention is paid to the thermodynamic stability of the A(x)C(60) phases. The calculations point out a phase separation in the doped fullerene layer into alkali-metal-rich and alkali-metal-depleted areas at room temperature. The final state is represented by two phases which coexist as a stable fine mixture of nanoscale particles. The instability of homogeneous layers has potentially critical impact on their electrical properties and can explain the formation of nanostructures (20-50 nm) at the fullerene-electrolyte interface. Rb(3)C(60) clusters are predicted to be larger than K(3)C(60) ones for equal mean alkali-metal concentrations. Experimental data on electrochemical metal deposition on alkali-metal-doped fullerene substrates-in particular, atomic force microscopy measurements-are also consistent with the model proposed.     

Temperature and pressure dependence of the rate constants of the reaction of NO3 radical with CH3SCH3

The reaction of nitrate radical with dimethyl sulfide was studied with cavity ring-down spectroscopy in 20-200 Torr of N2 diluent in the temperature range of 283-318 K. The rate constant for this reaction, k(1), is found to be temperature dependent and pressure independent: k1 = 4.5(-2.8)(+4.0) x 10(-13) exp[(310 +/- 220)/T] cm3 molecule(-1) s(-1). The uncertainties are two standard deviations from regression analyses. The present rate constants are in good agreement with those reported by Daykin and Wine (Int. J. Chem. Kinet. 1990, 22, 1083) and may be used in the atmospheric model calculation. Theoretical calculations were carried out to verify the existence of an intermediate complex.     

A comparison of two-component and four-component approaches for calculations of spin-spin coupling constants and NMR shielding constants of transition metal cyanides

Relativistic density functional theory (DFT) calculations of nuclear spin-spin coupling constants and shielding constants have been performed for selected transition metal (11th and 12th group of periodic table) and thallium cyanides. The calculations have been carried out using zeroth-order regular approximation (ZORA) Hamiltonian and four-component Dirac-Kohn-Sham (DKS) theory with different nonrelativistic exchange-correlation functionals. Two recent approaches for representing the magnetic balance (MB) between the large and small components of four-component spinors, namely, mDKS-RMB and sMB, have been employed for shielding tensor calculations and their results have been compared. Relativistic effects have also been analysed in terms of scalar and spin-orbit contributions at the two-component level of theory, including discussion of heavy-atom-on-light-atom effects for (1)J(CN), σ(C), and σ(N). The results for molecules containing metals from 4th row of periodic table show that relativistic effects for them are small (especially for spin-spin coupling constants). The biggest effects are observed for the 6th row where nonrelativistic theory reproduces only about 50%-70% of the two-component ZORA results for (1)J(MeC) and about 75% for heavy metal shielding constants. It is important to employ a full Dirac picture for calculations of heavy metal shielding constants, since ZORA reproduces only 75%-90% of the DKS results. Smaller discrepancies between ZORA-DFT and DKS are observed for nuclear spin-spin coupling constants. No significant differences are observed between the results obtained using mDKS-RMB and sMB approaches for magnetic balance in four-component calculations of the shielding constants.     

Determination of trace metal speciation parameters by using screen-printed electrodes in stripping chronopotentiometry without deaerating

The objective of this study was to exploit the advantages of stripping chronopotentiometry (SCP) and stripping chronopotentiometry at scanned deposition potential (SSCP) for trace metal speciation analyses by using thin-film mercury screen-printed electrodes (TMF-SPE). At first, the SCP parameters were optimised for TMF-SPE, in order to reach the complete depletion regime. It has been shown that a stripping current higher than or equal to 10 μA allows this regime to be attained without removing oxygen from the solution.Then, these analytical conditions were used for the construction of SSCP curves for Cd-PDCA and Cd-NTA. When the concentration of free ligand in solution was known, the knowledge of the model describing the SSCP curves in absence and presence of a complex and the use of an effective fitting tool enabled estimating the stability constant and the rate constants for complexation. Further studies with complexes of restricted mobility are however necessary to assess the usefulness of this procedure to also estimate the diffusion coefficient of the complexes. Besides, this study showed that this approach was valid even when ligands were not in excess at the electrode during stripping.