scholarly journals Unlocking Phase Diagrams for Molybdenum and Tungsten Nanoclusters and Prediction of their Formation Constants

2021 ◽  
Author(s):  
Enric Petrus ◽  
Carles Bo
Keyword(s):  
Phase Diagrams ◽  
General Rule ◽  
Formation Constants ◽  
Computational Method ◽  
Reaction Networks ◽  
Free Energies ◽  
Computational Approaches ◽  
Chemical Equilibria ◽  
Gibbs Energies ◽  
And Tungsten

Understanding and controlling aqueous speciation of metal oxides are key for the discovery and development of novel materials, and challenge both experimental and computational approaches. Here we present a computational method, called POMSimulator, which is able to predict speciation phase diagrams (Conc. vs pH) for multi-species chemical equilibria in solution, and which we apply to molybdenum and tungsten isopolyoxoanions (IPAs). Starting from the MO4 monomers, and considering dimers, trimers, and larger species, the chemical reaction networks involved in the formation of [H32Mo36O128]8- and [W12O42]12- are sampled in an automatic manner. This information is used for setting up ~105 speciation models, and from there, we generate the speciation phase diagrams, which show an insightful picture of the behavior of IPAs in aqueous solution. Furthermore, we predict the values for 107 formation constants for a diversity of molybdenum and tungsten molecular oxides. Among these species, we could include several pentagonal shaped species and very reactive tungsten intermediates as well. Last but not least, the calibration employed for correcting the DFT Gibbs energies is remarkably similar for both metals, which suggests that a general rule might exist for correcting computed free energies for other metals.<br>

scholarly journals Unlocking Phase Diagrams for Molybdenum and Tungsten Nanoclusters and Prediction of their Formation Constants

2021 ◽  
Author(s):  
Enric Petrus ◽  
Carles Bo
Keyword(s):  
Phase Diagrams ◽  
General Rule ◽  
Formation Constants ◽  
Computational Method ◽  
Reaction Networks ◽  
Free Energies ◽  
Computational Approaches ◽  
Chemical Equilibria ◽  
Gibbs Energies ◽  
And Tungsten

Understanding and controlling aqueous speciation of metal oxides are key for the discovery and development of novel materials, and challenge both experimental and computational approaches. Here we present a computational method, called POMSimulator, which is able to predict speciation phase diagrams (Conc. vs pH) for multi-species chemical equilibria in solution, and which we apply to molybdenum and tungsten isopolyoxoanions (IPAs). Starting from the MO4 monomers, and considering dimers, trimers, and larger species, the chemical reaction networks involved in the formation of [H32Mo36O128]8- and [W12O42]12- are sampled in an automatic manner. This information is used for setting up ~105 speciation models, and from there, we generate the speciation phase diagrams, which show an insightful picture of the behavior of IPAs in aqueous solution. Furthermore, we predict the values for 107 formation constants for a diversity of molybdenum and tungsten molecular oxides. Among these species, we could include several pentagonal shaped species and very reactive tungsten intermediates as well. Last but not least, the calibration employed for correcting the DFT Gibbs energies is remarkably similar for both metals, which suggests that a general rule might exist for correcting computed free energies for other metals.<br>

scholarly journals The SN2 reaction and its relationship with the Walden inversion, the Finkelstein and Menshutkin reactions together with theoretical calculations for the Finkelstein reaction

2021 ◽  
Author(s):  
Ibon Alkorta ◽  
José Elguero
Keyword(s):  
Linear Models ◽  
Theoretical Calculations ◽  
Computational Method ◽  
Basis Set ◽  
Free Energies ◽  
Nitrogen And Phosphorus ◽  
Atom Pairs ◽  
Leaving Groups ◽  
First Time ◽  
Nitrogen Phosphorus

AbstractThis communication gives an overview of the relationships between four reactions that although related were not always perceived as such: SN2, Walden, Finkelstein, and Menshutkin. Binary interactions (SN2 & Walden, SN2 & Menshutkin, SN2 & Finkelstein, Walden & Menshutkin, Walden & Finkelstein, Menshutkin & Finkelstein) were reported. Carbon, silicon, nitrogen, and phosphorus as central atoms and fluorides, chlorides, bromides, and iodides as lateral atoms were considered. Theoretical calculations provide Gibbs free energies that were analyzed with linear models to obtain the halide contributions. The M06-2x DFT computational method and the 6-311++G(d,p) basis set have been used for all atoms except for iodine where the effective core potential def2-TZVP basis set was used. Concerning the central atom pairs, carbon/silicon vs. nitrogen/phosphorus, we reported here for the first time that the effect of valence expansion was known for Si but not for P. Concerning the lateral halogen atoms, some empirical models including the interaction between F and I as entering and leaving groups explain the Gibbs free energies.

Ideal Solutions

1993 ◽  
Author(s):  
Greg M. Anderson ◽  
David A. Crerar
Keyword(s):  
Chemical Constituents ◽  
Physical Nature ◽  
Mechanical Mixture ◽  
The Other ◽  
Free Energies ◽  
Gibbs Energies ◽  
Ideal Solutions ◽  
Solution Reaction ◽  
Spontaneous Reaction ◽  
Trace Components

The chemical constituents of a solution can be varied — added, subtracted and interchanged or substituted for each other — within limits ranging from complete (e.g., gases) to highly restricted (trace components in quartz). Adding or subtracting chemical constituents to or from a phase involves changes in energy, which will be discussed in the following sections. For example, if two components A and B are mixed together, the Gibbs energy of a solution of the two mixed must be less than the sum of the Gibbs energies of the two separately for the spontaneous reaction to take place. That is, if we mix nA moles of component A and nA moles of component B, their combined total G is (nAGA + nBGB) where GA and GB are the molar free energies of A and B. If G(A,B) is the total free energy of the resulting solution, then necessarily if the solution took place spontaneously. Alternatively, dividing through by nA + nB, where XA and XB are the mole fractions. Thus if A is albite and B is anorthite, then (A,B) is plagioclase, and we say that the plagioclase solid solution is more stable than a "mechanical mixture" of grains of albite and anorthite. On the other hand if A is diopside and B is anorthite, little or no mutual solution takes place because in this case so that no spontaneous solution reaction takes place. The term "mechanical mixture" in this context nicely conveys the idea of quantities of mineral grains mixed together and not reacting, but does not work quite so well if A and B are other things such as water and halite, or water and alcohol. Nevertheless, the term is traditionally used no matter what the nature of the solution constituents, and no harm is done as long as we remember that "mechanical mixture" means that the constituents considered do not react with each other, whatever their physical nature.

Polymer + Solvent Systems: Phase Diagrams, Interface Free Energies, and Nucleation

2005 ◽  
pp. 1-110 ◽  
Author(s):  
Kurt Binder ◽  
Marcus Müller ◽  
Peter Virnau ◽  
Luis González MacDowell
Keyword(s):  
Phase Diagrams ◽  
Free Energies ◽  
Solvent Systems ◽  
Polymer Solvent

Gibbs energies of transfer of individual ions from water to acetone + water solvents

1989 ◽  
Vol 67 (8) ◽  
pp. 1268-1273 ◽  
Author(s):  
Mahmoud Mohamad Elsemongy ◽  
Ahmed Ahmed Abdel-Khalek
Keyword(s):  
Glass Electrode ◽  
Aqueous Mixtures ◽  
Free Energies ◽  
Emf Measurements ◽  
Gibbs Energies ◽  
Electrode Potentials ◽  
Gibbs Energies Of Transfer ◽  
Acetone Water ◽  
Alkali Metal Halides ◽  
Dipolar Aprotic Solvents

The standard absolute potentials of hydrogen, Ag–AgX (X = Cl, Br, and I) and M/M+ (M = Li, Na, K, Rb, and Cs) electrodes in nine different acetone + water solvents containing up to 80 wt. % acetone were determined from the emf data at 25 °C of the cells: glass electrode/HCl (m), solvent/AgCl–Ag and glass electrode (M)/MX (m), solvent/AgX–Ag. The standard Gibbs free energies of a transfer of halogen acids and alkali metal halides as well as their constituent individual ions from water to the respective solvents were computed. The observed increases in [Formula: see text] values of all ions with increasing acetone content of the solvent and their relative order in each solvent were interpreted and discussed. A comparison of the present results with those obtained earlier in the dimethyl sulphoxide (DMSO) + water solvents shows the different nature of the two dipolar aprotic solvents, acetone and DMSO, in their aqueous mixtures. Keywords: acetone + water solvents, electrode potentials, emf measurements, individual ions, transfer free energies.

scholarly journals Thermodynamically Consistent Estimation of Gibbs Free Energy from Data: Data Reconciliation Approach

2018 ◽  
Author(s):  
Saman Salike ◽  
Nirav Bhatt
Keyword(s):  
Experimental Data ◽  
Free Energy ◽  
Gibbs Free Energy ◽  
Measurement Errors ◽  
Optimization Problems ◽  
Data Reconciliation ◽  
Group Contributions ◽  
Free Energies ◽  
Consistent Estimation ◽  
Gibbs Energies

AbstractMotivationThermodynamic analysis of biological reaction networks requires the availability of accurate and consistent values of Gibbs free energies of reaction and formation. These Gibbs energies can be measured directly via the careful design of experiments or can be computed from the curated Gibbs free energy databases. However, the computed Gibbs free energies of reactions and formations do not satisfy the thermodynamic constraints due to the compounding effect of measurement errors in the experimental data. The propagation of these errors can lead to a false prediction of pathway feasibility and uncertainty in the estimation of thermodynamic parameters.ResultsThis work proposes a data reconciliation framework for thermodynamically consistent estimation of Gibbs free energies of reaction, formation and group contributions from experimental data. In this framework, we formulate constrained optimization problems that reduce measurement errors and their effects on the estimation of Gibbs energies such that the thermodynamic constraints are satisfied. When a subset of Gibbs free energies of formations is unavailable, it is shown that the accuracy of their resulting estimates is better than that of existing empirical prediction methods. Moreover, we also show that the estimation of group contributions can be improved using this approach. Further, we provide guidelines based on this approach for performing systematic experiments to estimate unknown Gibbs formation energies.AvailabilityThe MATLAB code for the executing the proposed algorithm is available for free on the GitHub repository:https://github.com/samansalike/[email protected]

scholarly journals CONDUCTOMETRIC STUDY OF COMPLEX FORMATION BETWEEN 2,3-PYRAZINEDICARBOXYLIC ACID AND SOME TRANSITION METAL IONS IN METHANOL

2012 ◽  
Vol 20 (20) ◽  
pp. 43-50
Author(s):  
A.A. El-Khouly ◽  
E. A. Gomaa ◽  
S. E. Salem
Keyword(s):  
Complex Formation ◽  
Transition Metal Ions ◽  
Formation Constants ◽  
Molar Conductance ◽  
Association Constants ◽  
Absolute Methanol ◽  
Free Energies ◽  
Titration Curves ◽  
Conductometric Study ◽  
Complexation Reactions

The complexation reactions between CuCl2 CoCL2 and NiCL2 with 2,3-Pyrazinedicarboxylic acid in methanol (MeOH) at 313.15 K were studied by conductometric methods. The association constants, formation constants and Gibbs free energies were calculated from the conduclometric titration curves. On drawing the relation between molar conductance and the ratio of metal to ligand coflCentrations, different lines were obtained indicating the formation of 1: 1 and 2: 1 (M:L) stoichiometric complexes. The formation constants and Gibbs free energies of different complexes in absolute Methanol at 313.15 Kfollow the order:

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