Brick by brick computation of the gibbs free energy of reaction in solution using quantum chemistry and COSMO‐RS

Hellweg, Arnim; Eckert, Frank

doi:10.1002/aic.15716

Cited by 62 publications

(62 citation statements)

References 90 publications

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“…The solution equilibrium for the relevant gallium and zinc species in the aqueous and organic phases as calculated at COSMO-RS-FINE/RI-MP2 level. [34] The values are in kcal/mol. extraction of Ga into the C4-C7 ethers measured for both high (5.6 M) and low (1 M) ZnCl 2 concentrations in 6 M HCl as evidenced by a mean unsigned error of prediction (MUE, 2.8% and 4.0% correspondingly).…”

Section: +mentioning

confidence: 99%

Separation of Radiogallium from Zinc Using Membrane-Based Liquid-Liquid Extraction in Flow: Experimental and COSMO-RS Studies

Pedersen

Nielsen

Fonslet

et al. 2019

Solvent Extraction and Ion Exchange

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A switch from batch to continuous manufacturing of gallium-68 (68 Ga) and 68 Ga-labeled pharmaceuticals can be advantageous, as it recycles isotopically-enriched zinc-68 (68 Zn), removes pre-and post-irradiation target manipulations, and provides scalability via dose-on-demand production. Herein we report efficient extraction of radiogallium (66,67,68 Ga = *Ga) from ZnCl 2 /HCl solutions in batch and in flow using a membrane-based liquidliquid separator. From 5.6 M ZnCl 2 /3 M HCl, a 1/2 (v/v) diisopropyl ether (i Pr 2 O)/trifluorotoluene (TFT) solvent extracts 76.3 ± 1.9% of *Ga and 1.9 ± 1.6% of Zn in flow using a single pass through. From 1 M ZnCl 2 /6 M HCl, a 1/2 (v/v) n-butyl methyl ether (n-BuOMe)/TFT solvent extracts 95.7 ± 2.0% of *Ga and 0.005 ± 0.003% of Zn in flow. TFT plays a key role in controlling the interfacial tension between the aqueous and the organic phases, ensuring clean membrane-based separation. The process did not extract Cu, Mn, and Co but did extract Fe. Using HGaCl 4 and ZnCl 2 as the extractable species, the COSMO-RS theory predicts the solvation-driven extraction of Ga and Zn with a mean unsigned error of prediction of 4.0% and 3.4% respectively. KEYWORDS Gallium-68; gallium-67; liquid-liquid extraction in flow; COSMO-RS 68 Ge/ 68 Ga-generators further contribute to 68 Ga popularity in clinical and pre-clinical settings. [6] Meeting the growing demand for 68 Ga is a challenge, as it is mostly supplied by the gallium generators which suffer from high prices, long lead time, quality inconsistencies, and limited shelf life. [7] An alternative method of 68 Ga production is the irradiation of 68 Zn using a cyclotron. [8] Since many PET-centers have their own cyclotrons, this is potentially a convenient means of in-house production of 68 Ga-tracers. However, the cyclotron production of 68 Ga in solid targets from 68 Zn

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Section: +mentioning

confidence: 99%

Separation of Radiogallium from Zinc Using Membrane-Based Liquid-Liquid Extraction in Flow: Experimental and COSMO-RS Studies

Pedersen

Nielsen

Fonslet

et al. 2019

Solvent Extraction and Ion Exchange

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“…Various thermodynamic cycles have been proposed earlier to evaluate Gibbs free energy of solvation [Δ G (solvation) ] or “solvation free energies” in different solvents. Phenomenologically, the process of adduct formation in presence of a solvent can be assumed to have taken place through the following steps: A (solvated) → A + solvent (i.e., desolvation of the acceptor) B (solvated) → B + solvent (i.e., desolvation of the donor) A + B → AB (i.e., adduct formation) AB + solvent → AB (solvated) (solvation of the adduct) …”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…Δ G X (solvation) represent the corresponding Gibbs free energy of solvation (where X = A, B, or AB). From Equation , an analogy can be drawn that the “net desolvation energy,”

{normalΔ E}_{desolv}^{net}

, is equal to the “net free energy of solvation,”

{normalΔ G}_{(solvayion)}^{net}

with negative sign (also called the “binding free energy’”) as shown below:

\begin{matrix} true \\ {Δ E}_{desolv}^{net} = [(E_{A (gas)} + E_{B (gas)}) - E_{AB (gas)}] - [(E_{A (solvent)} + E_{B (solvent)}) - E_{AB (solvent)}] \\ = - B . E ._{((), gas)} + B . E ._{((), solvent)} = B . E ._{((), solvent)} - B . E ._{((), gas)} = Binding free energy \end{matrix}

…”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…Various thermodynamic cycles have been proposed earlier [23][24][25] to evaluate Gibbs free energy of solvation [ΔG (solvation) ] or "solvation free energies" in different solvents. Phenomenologically, the process of adduct formation in presence of a solvent can be assumed to have taken place through the following steps: From, thermodynamic consideration step (i) and step (ii) are endothermic processes as energy is required to overcome the attractive interaction between either A or B and the solvent (in the process of desolvation).…”

Section: Working Equations To Take Care Of Solvent Effect In Stabilmentioning

confidence: 99%

“…ΔG X(solvation) represent the corresponding Gibbs free energy of solvation (where X = A, B, or AB). From Equation 9, an analogy can be drawn that the "net desolvation energy," ΔE net desolv , is equal to the "net free energy of solvation," ΔG net solvayion ð Þ with negative sign [25] (also called the "binding free energy'") [19] as shown below:…”

Section: Working Equations To Take Care Of Solvent Effect In Stabilmentioning

confidence: 99%

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Solvent effect on stabilization energy: An approach based on density functional reactivity theory

Hamid

Roy

2019

Int J of Quantum Chemistry

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In the present article a formalism and the corresponding computational method is developed to take care of the variation of stabilization energy with solvent polarity in the process of adduct formation. For this purpose, a simple but physically insightful definition of “net desolvation energy” is proposed keeping in mind the sequence of events taking place in the process of adduct formation in a solvent. The approach used here is based on density functional reactivity theory (DFRT) and the representative samples chosen are adduct formation between (a) methyltrioxorhenium (MTO) and pyridine and (b) (azidomethyl)benzene and methylpropiolate. The generated data in case (a) is correlated with already known experimental parameter that is, formation constant (Kf). The observed trends claim that with the increase in solvent polarity interaction (or stabilization) energy becomes less negative which means that on increasing the solvent polarity the chances of adduct formation are less. This is further supported by calculating hardness values of adducts in different solvents which goes on decreasing with the increase in solvent polarity. Here, the computed data show that on increasing the polarity (i.e., dielectric constant) of the solvent, the “net desolvation energy” increases. Finally, when “net desolvation energy” is added to the stabilization energy obtained from DFRT the predicted trends are achieved.

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Effect of surface curvature and wettability on nucleation of methane hydrate

Fan

Wang

et al. 2022

AIChE Journal

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Natural gas hydrate nucleation is a complex physical and chemical process that is not well understood presently. In this article, an improved thermodynamic model is proposed to analyze the effects of surface curvature and wettability on methane hydrate nucleation for the first time. The results indicate that methane hydrate nucleation is more difficult on hydrophilic curvature surfaces under the same conditions, with a larger critical nucleation radius and required energy barrier than on hydrophobic surfaces. Furthermore, a convex surface is more favorable for forming methane hydrate under the same conditions than a concave surface. The model's results are critical in elucidating the microscopic mechanism of methane hydrate nucleation and providing a theoretical foundation for developing technologies for strengthening and inhibiting hydrate formation.

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Brick by brick computation of the gibbs free energy of reaction in solution using quantum chemistry and COSMO‐RS

Cited by 62 publications

References 90 publications

Separation of Radiogallium from Zinc Using Membrane-Based Liquid-Liquid Extraction in Flow: Experimental and COSMO-RS Studies

Separation of Radiogallium from Zinc Using Membrane-Based Liquid-Liquid Extraction in Flow: Experimental and COSMO-RS Studies

Solvent effect on stabilization energy: An approach based on density functional reactivity theory

Effect of surface curvature and wettability on nucleation of methane hydrate

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