Application of a Chemical Thermodynamic Model to the Gibbs Free Energy of Aqueous Electrolyte Solutions. New Equations for the Activity and Osmotic Coefficients

1991 ◽  
Vol 44 (9) ◽  
pp. 1195
Author(s):  
JV Leyendekkers
Keyword(s):  
Free Energy ◽  
Gibbs Free Energy ◽  
Short Range ◽  
Van Der Waals ◽  
Osmotic Coefficients ◽  
Electrolyte Solutions ◽  
Solute Concentration ◽  
Volume Effect ◽  
Chemical Thermodynamic ◽  
Short Range Repulsion

The chemical thermodynamic (CT) model, based on the extended Tait equation, has been applied to the Gibbs free energy of aqueous solutions of sodium chloride and potassium chloride at 25°C. Equations for the activity and osmotic coefficients were derived. These are made up of the Debye-Huckel limiting slope term, a van der Waals co-volume effect term covering short-range repulsion, a term covering the water compression by the solute and a short-range attractive term. The distance of closest approach derived from the model is the same as that expected for the van der Waals effect. The individual components of the partial molal free energy, that is, the effects of solute concentration on the water and solute respectively, have been calculated.

Chemical equilibrium and chemical kinetics

2018 ◽  
Author(s):  
Dennis Sherwood ◽  
Paul Dalby
Keyword(s):  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Chemical Kinetics ◽  
Chemical Equilibrium ◽  
First Principles ◽  
Effect Of Temperature ◽  
Total System ◽  
Free Energies

Building on the previous chapter, this chapter examines gas phase chemical equilibrium, and the equilibrium constant. This chapter takes a rigorous, yet very clear, ‘first principles’ approach, expressing the total Gibbs free energy of a reaction mixture at any time as the sum of the instantaneous Gibbs free energies of each component, as expressed in terms of the extent-of-reaction. The equilibrium reaction mixture is then defined as the point at which the total system Gibbs free energy is a minimum, from which concepts such as the equilibrium constant emerge. The chapter also explores the temperature dependence of equilibrium, this being one example of Le Chatelier’s principle. Finally, the chapter links thermodynamics to chemical kinetics by showing how the equilibrium constant is the ratio of the forward and backward rate constants. We also introduce the Arrhenius equation, closing with a discussion of the overall effect of temperature on chemical equilibrium.

scholarly journals Adsorption in Mixtures with Competing Interactions

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4532
Author(s):  
Marek Litniewski ◽  
Alina Ciach
Keyword(s):  
Short Range ◽  
Selective Adsorption ◽  
Similar Amount ◽  
Particle Interactions ◽  
Near Surface ◽  
Gas Density ◽  
Short Range Repulsion ◽  
Adsorbed Layers ◽  
Dynamics Simulations ◽  
Oppositely Charged

A binary mixture of oppositely charged particles with additional short-range attraction between like particles and short-range repulsion between different ones in the neighborhood of a substrate preferentially adsorbing the first component is studied by molecular dynamics simulations. The studied thermodynamic states correspond to an approach to the gas–crystal coexistence. Dependence of the near-surface structure, adsorption and selective adsorption on the strength of the wall–particle interactions and the gas density is determined. We find that alternating layers or bilayers of particles of the two components are formed, but the number of the adsorbed layers, their orientation and the ordered patterns formed inside these layers could be quite different for different substrates and gas density. Different structures are associated with different numbers of adsorbed layers, and for strong attraction the thickness of the adsorbed film can be as large as seven particle diameters. In all cases, similar amount of particles of the two components is adsorbed, because of the long-range attraction between different particles.

Extended Gibbs Free Energy and Laplace Pressure of Ordered Hexagonal Close-Packed Spherical Particles: A Wettability Study

Langmuir ◽  
2021 ◽  
Author(s):  
Amir Bayat ◽  
Mahdi Ebrahimi ◽  
Saeed Rahemi Ardekani ◽  
Esmaiel Saievar Iranizad ◽  
Alireza Zaker Moshfegh
Keyword(s):  
Free Energy ◽  
Gibbs Free Energy ◽  
Laplace Pressure ◽  
Spherical Particles ◽  
Hexagonal Close Packed

scholarly journals First-Principles Study of Mechanical and Thermodynamic Properties of Binary and Ternary CoX (X = W and Mo) Intermetallic Compounds

Materials ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1404
Author(s):  
Yunfei Yang ◽  
Changhao Wang ◽  
Junhao Sun ◽  
Shilei Li ◽  
Wei Liu ◽  
...  
Keyword(s):  
Free Energy ◽  
Thermodynamic Properties ◽  
Gibbs Free Energy ◽  
Density Functional ◽  
Vibrational Entropy ◽  
Functional Theory ◽  
Lattice Constants ◽  
The Density Functional Theory ◽  
Ductile Behavior ◽  
Pseudo Potential

In this study, the structural, elastic, and thermodynamic properties of DO19 and L12 structured Co3X (X = W, Mo or both W and Mo) and μ structured Co7X6 were investigated using the density functional theory implemented in the pseudo-potential plane wave. The obtained lattice constants were observed to be in good agreement with the available experimental data. With respect to the calculated mechanical properties and Poisson’s ratio, the DO19-Co3X, L12-Co3X, and μ-Co7X6 compounds were noted to be mechanically stable and possessed an optimal ductile behavior; however, L12-Co3X exhibited higher strength and brittleness than DO19-Co3X. Moreover, the quasi-harmonic Debye–Grüneisen approach was confirmed to be valid in describing the temperature-dependent thermodynamic properties of the Co3X and Co7X6 compounds, including heat capacity, vibrational entropy, and Gibbs free energy. Based on the calculated Gibbs free energy of DO19-Co3X and L12-Co7X6, the phase transformation temperatures for DO19-Co3X to L12-Co7X6 were determined and obtained values were noted to match well with the experiment results.

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