Gibbs-duhem-margules laws

Gokcen, N. A.

doi:10.1007/bf02648369

Cited by 42 publications

(27 citation statements)

References 6 publications

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“…Therefore it is not surprising when Haase [17] (p. 360) showed that the polynomial nowadays ascribed to Redlich and Kister is completely identical with the conventional ansatz of Margules. The same was later underlined by others ( [7], p. 225; [18]). This very fact throws a questionable light on the authorship of Redlich and Kister.…”

Section: Practical Consequencessupporting

confidence: 60%

Chemical Potential vs. Gibbs Free Energy Relationship by Redlich and Kister and the Redlich-Kister Polynomial

Näfe¹

2014

Int. J. Thermo

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The relationship of Redlich and Kister between the chemical potential and the molar Gibbs free energy of a multicomponent mixture proves to be in contradiction with both fundamental concepts of chemical thermodynamics and mathematical principles. Hence, it is invalid. This invalidity corresponds with the thermodynamically inadequate representation of the prevalent Redlich-Kister polynomial for the mole fraction dependence of the excess Gibbs free energy of a mixture.

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Section: Practical Consequencessupporting

confidence: 60%

Chemical Potential vs. Gibbs Free Energy Relationship by Redlich and Kister and the Redlich-Kister Polynomial

Näfe¹

2014

Int. J. Thermo

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“…In a binary system, the only requirement for a thermodynamically sound activity coefficient model is satisfying the Duhem-Margules relation (Eq. 11), which implies conformance with the more familiar Gibbs-Duhem relation (Margules, 1895;McGlashan, 1963;Gokcen, 1996);…”

Section: Bat Activity Coefficient Modelsupporting

confidence: 57%

RH-dependent organic aerosol thermodynamics via an efficient reduced-complexity model

Gorkowski

Preston

Zuend

2019

Preprint

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Water plays an essential role in aerosol chemistry, gas-particle partitioning, and particle viscosity, but it is typically omitted in thermodynamic models describing the mixing within organic aerosol phases and the partitioning of semivolatile organics. In this study, we introduce the Binary Activity Thermodynamics (BAT) model, a water-sensitive, reduced-complexity model treating the non-ideal mixing of water and organics. The BAT model can process different levels of physicochemical mixture information enabling its application in the thermodynamic aerosol treatment within chemical transport models, the 5 evaluation of humidity effects in environmental chamber studies, and the analysis of field observations. It is capable of using organic structure information including O : C, H : C, molar mass, and vapor pressure, which can be derived from identified compounds or estimated from bulk aerosol properties. A key feature of the BAT model is predicting the extent of liquid-liquid phase separation occurring within aqueous mixtures containing hydrophobic organics. This is crucial to simulating the abrupt change in water uptake behavior of moderately hygroscopic organics at high relative humidity, which is essential for capturing 10 the correct behavior of organic aerosols serving as cloud condensation nuclei. For gas-particle partitioning predictions, we complement a Volatility Basis Set (VBS) approach with the BAT model to account for non-ideality and liquid-liquid equilibrium effects. To improve the computational efficiency of this approach, we trained two neural networks; the first for the prediction of aerosol water content at given relative humidity, and the second for the partitioning of semivolatile components.The integrated VBS + BAT model is benchmarked against high-fidelity molecular-level gas-particle equilibrium calculations 15 based on the AIOMFAC model. Organic aerosol systems derived from α-pinene or isoprene oxidation are used for comparison.Predicted organic mass concentrations agree within less than a 5 % error in the isoprene case, which is a significant improvement over a traditional VBS implementation. In the case of the α-pinene system, the error is less than 2 % up to a relative humidity of 94 %, with larger errors past that point. The goal of the BAT model is to represent the bulk O : C and molar mass dependencies of a wide range of water-organic mixtures to a reasonable degree of accuracy. In this context, we discuss that 20 the reduced-complexity effort may be poor at representing a specific binary water-organic mixture perfectly. However, the averaging effects of our reduced-complexity model become more representative when the mixture diversity increases in terms of organic functionality and number of components.

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“…0 produced by the set of solvent molecules which are in surface-contact with the reactants and products. Then, the Margules equations [19] suggest ln(g solute ) = x(x solvent ) 2 ( Figure S6a in the Supporting Information), which leads to the solute activity a solute ¼ g solute The molecular interpretation of the latter DG S exch contribution is difficult and challenging, which probably explains the so far limited impact produced by the report of Equation (6) in 2013.…”

Section: Exchange Of Neutral [La(hfa) 3 ]G Uest Betweendiglyme and L1mentioning

confidence: 99%

“…(4)) for each different mixture along the titration.T he physicalo rigin of this effect, often neglected in biology and in coordination chemistry, [18] can be traced back to the regular solutiont heory of binary mixtures, in which Margules equations [19] predict that the activity coefficients of the solute obeys ln(g solute ) = x(x solvent ) 2 ,w here x solvent is the solvent mole fraction and x is ad imensionlessp arameter that is a measureo ft he energy of solute-solvent interactions relative to solute-solute and solvent-solvent interactions. (4)) for each different mixture along the titration.T he physicalo rigin of this effect, often neglected in biology and in coordination chemistry, [18] can be traced back to the regular solutiont heory of binary mixtures, in which Margules equations [19] predict that the activity coefficients of the solute obeys ln(g solute ) = x(x solvent ) 2 ,w here x solvent is the solvent mole fraction and x is ad imensionlessp arameter that is a measureo ft he energy of solute-solvent interactions relative to solute-solute and solvent-solvent interactions.…”

Section: Introductionmentioning

confidence: 99%

Chemical Potential of the Solvent: A Crucial Player for Rationalizing Host–Guest Affinities

Baudet

Guerra

Piguet

2017

Chemistry A European J

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Access to reliable values of the thermodynamic constants β1,1H,G , which control simple host-guest ([HG]) association, is crucial in medicine, biology, pharmacy, and chemistry, since the optimum concentration of an effector (i.e., a drug) acting on a receptor is set to 1β1,1H,G . Intermolecular association between charged species in polar solvents, for which water is the archetype, largely obeys this principle. Any deviation from ideality, which alters the speciation in solution, is mastered by the Debye-Hückel theory of ionic atmosphere. Much less is known for related association reactions involving neutral species in non-polar (lipophilic) media such as membranes, bilayers, or organic polymers. Taking the intermolecular association between [La(hfa) dig] guest (hfa=hexafluoroacetylacetonate, dig=2-{2-methoxyethoxy}ethane) and tridentate polyaromatic host receptors L1-L3 in dichloromethane as a proof-of-concept, we show that the progress of the association reactions, as measured by the increase in the mole fraction of occupied sites of the receptors, disrupt the chemical potential of the solvent to such an extent that β1,1H,G may seemingly be shifted by two orders of magnitude, thus leading to erroneous dose-response prescriptions. A simple chemical model, which considers a subset of solvent molecules in surface contact with the partners of the association reaction, restores reliable access to true and interpretable thermodynamic constants. The concomitant emergence of a concentration-dependent corrective parameter reestablishes satisfying dose-dependent response under real conditions. This "complement" to the law of mass action offers a simple method for safely taking care of the non-predictable variations of the activity coefficients of the various partners when host-guest reactions are conducted in non-polar media.

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Gibbs-duhem-margules laws

Cited by 42 publications

References 6 publications

Chemical Potential vs. Gibbs Free Energy Relationship by Redlich and Kister and the Redlich-Kister Polynomial

Chemical Potential vs. Gibbs Free Energy Relationship by Redlich and Kister and the Redlich-Kister Polynomial

RH-dependent organic aerosol thermodynamics via an efficient reduced-complexity model

Chemical Potential of the Solvent: A Crucial Player for Rationalizing Host–Guest Affinities

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