Academic literature on the topic 'Thermodynamic modelling using COSMO-RS'

To properly design ionic liquids (ILs) adopted for gases separation uses, a knowledge of ILs thermodynamic properties as well their solubilities with the gases is essential. In the present article, solubilities of CO2 and H2S in bis(2-Ethylhexyl)sulfosuccinate based ILs were predicted using the conductor like screening model for real solvents COSMO-RS. According to COSMO-RS calculations, the influence of the cation change was extensively analyzed. The obtained data are used for the prediction of adequate solvent candidates. Moreover, to understand the intrinsic behavior of gases solubility the free volume of the chosen ILs and their molecular interactions with respectively CO2 and H2S were computed. The results suggest that hydrogen bonding interactions in ILs and between ILs and the gases have a pivotal influence on the solubility.

Liquid–liquid equilibrium (LLE) data are critical for the design and optimization of processes for extracting aromatics. Partial LLE data for the non-aromatic–aromatic–sulfolane ternary system were acquired at 313.15 K and 101.3 kPa. The LLE data for the extraction of aromatics using sulfolane were predicted using the COSMO-RS model. Correspondingly, the predicted and experimental data were analyzed using the root mean square deviation (RMSD), distribution coefficient (D), and separation factor (S). The COSMO-RS model could better predict the LLE data for the extraction of aromatics by sulfolane. The results of quantum chemical calculation show that hydrogen bonds and van der Waals interactions between sulfolane–benzene and sulfolane–toluene were responsible for the strong selectivity of sulfolane for benzene and toluene over alkanes. The LLE data predicted by the COSMO-RS method using the UNIQUAC thermodynamic model were subjected to correlation analysis. The calculated RMSD values were all less than 0.0180, and the relative deviation (δ) between the simulated value of the main process index for the extraction column and the actual data was less than 2.5%, indicating that the obtained binary interaction parameters can be reliably used in designing and optimizing the extraction of aromatics using sulfolane.

Abstract. We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and α,ω-dicarboxylic acids and water in binary acid–water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. COnductor-like Screening MOdel for Real Solvents (COSMO-RS) underestimates experimental monocarboxylic acid activity coefficients by less than a factor of 2, but experimental water activity coefficients are underestimated more especially at high acid mole fractions. We found a better agreement between COSMOtherm-estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation, and reaction extension (COSMO-RS-DARE) of COSMOtherm. COSMO-RS-DARE is not fully predictive, but fit parameters found here for water–water and acid–water clustering interactions can be used to estimate thermodynamic properties of monocarboxylic acids in other aqueous solvents, such as salt solutions. For the dicarboxylic acids, COSMO-RS is sufficient for predicting aqueous solubility and activity coefficients, and no fitting to experimental values is needed. This is highly beneficial for applications to atmospheric systems, as these data are typically not available for a wide range of mixing states realized in the atmosphere, due to a lack of either feasibility of the experiments or sample availability. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C5–C8), while for monocarboxylic acids (C1–C6) and smaller dicarboxylic acids (C2–C4), hydrate formation is more favorable, especially in dilute solutions.

Abstract This work presents a judicious screening of 986 possible ionic liquid (IL) combinations for the removal of Endosulfan using COSMO-RS (Conductor-like Screening Model for Real Solvents) model. Initially, benchmarking studies have been carried out for α-Endosulfan, β-Endosulfan, Endosulfan sulfate, Endosulfan-alcohol, Endosulfan lactone, and Endosulfan ether by comparing COSMO-RS experimental and predicted octanol–water partition coefficients. Thereafter, COSMO-RS selectivity predictions were done on 986 ionic liquid combinations at infinite dilution. The order of selectivity for the five cation groups were found to be as follows: [TBP] > [TIBMP] > [TBMP] > [C2DMIM] > [BEPYR] > [DPPYR] > [C4DMIM] > [C8MPY] > [BTNH] > [BETNH]. Highest selectivity was obtained for phosphonium based IL namely: [TBP][TOS] (212.5). Anions such as [C8H17SO4], [Br], [Sal], [TOS], [MDEGSO4], and [DEC] contributed high selectivities because of the absence of sterical shielding effect around their charge centers. Further capacity and the performance index (PI) values were calculated and predicted along with selectivity. The increasing order of performance index values were found to follow: [TBP][Sal] (1.71+E5) > [DPPYR][Br] (1.07+E6) > [C2DMIM] (1.01+E6) > [C8MPY][Cl] (1.6+E5) > [BETNH][DEC] (1.2+E5).

The electrostatic – misfit energy arise from repulsive interaction of CH₄ plays a dominant role in determining its solubility in ILs. Modelling using COSMO-RS shows that IL size and van der Walls forces only have marginal influences on CH₄ solubility.

The solubility of dehydroabietic acid in (−)-α-pinene, p-cymene, (−)-β-caryophyllene, (−)-α-pinene + p-cymene, (−)-β-caryophyllene + p-cymene and (−)-α-pinene + (−)-β-caryophyllene were determined using the laser monitoring method at atmospheric pressure. The solubility of dehydroabietic acid was positively correlated with temperature from 295.15 to 339.46 K. (−)-α-pinene, p-cymene, and (−)-β-caryophyllene were found to be suitable for the solubilization of dehydroabietic acid. In addition, the non-random two liquid (NRTL), universal quasi-chemical (UNIQUAC), modified Apelblat, modified Wilson, modified Wilson–van’t Hoff, and λh models were applied to correlate the determined solubility data. The modified Apelblat model gave the minor deviation for dehydroabietic acid in monosolvents, while the λh equation showed the best result in the binary solvents. A comparative analysis of compatibility between solutes and solvents was carried out using Hansen solubility parameters. The thermodynamic functions of ΔsolH0, ΔsolS0, ΔsolG0 were calculated according to the van’t Hoff equation, indicating that the dissolution was an entropy-driven heat absorption process. The Conductor-like Screening Model for Real Solvents (COSMO-RS) combined with an experimental value was applied to predict the reasonable solubility data of dehydroabietic acid in the selected solvents systems. The interaction energy of the dehydroabietic acid with the solvent was analyzed by COSMO-RS.

Solubility of active pharmaceutical ingredients is an important aspect of drug processing and formulation. Although caffeine was a subject of many studies aiming to quantify saturated solutions, many applied solvents suffer from not being environmentally friendly. This work fills this gap by presenting the results of solubility measurements in choline chloride natural deep eutectic solvents, ccNADES, comprising one of seven of the following polyalcohols: glycerol, sorbitol, xylitol, glucose, sucrose, maltose and fructose. The ratio of ccNADES components was optimized for maximizing caffeine solubility at room temperature. Additionally, temperature dependent solubility was measured for the first four systems exhibiting the highest solubility potential, both in their neat forms and in mixtures with water. Results were used for intermolecular interactions assessments using the COSMO-RS-DARE approach, which led to a perfect match between experimental and computed solubility values. An important methodological discussion was provided for an appropriate definition of the systems. Surprising linear trends were observed between the values of fitting parameters and water-ccNADES composition. In addition, comments on selection of the values of the fusion thermodynamic parameters were provided, which led to the conclusion that COSMO-RS-DARE solubility computations can effectively compensate for the inaccuracies of these important physicochemical properties.

Les extraits naturels de plantes sont des ingrédients précieux pour un large éventail d'applications, notamment dans les industries cosmétiques ou pharmaceutiques ou dans les industries des parfums ou alimentaires. Mais l'extraction de ces composés naturels reste majoritairement réalisée à l'aide de solvants organiques volatils (COV) et de procédés ayant des impacts environnementaux importants. Dans le contexte récent de la chimie verte et de l'éco-extraction, des solvants alternatifs durables ont été développés pour remplacer les COV. Parmi ces solvants, les solvants biosourcés (BioSol), les solvants eutectiques profonds (DES) et les liquides ioniques (IL) ont fait l'objet d'intenses études au cours des deux dernières décennies. Néanmoins, les développements actuels des techniques d'extraction végétale reposent majoritairement sur des essais expérimentaux, ce qui limite le nombre de conditions et de solvants d'extraction pouvant être évalués. Pour remédier à cette limitation, plusieurs outils de modélisation ont été développés pour prédire les propriétés des solvants et soutenir le choix des solvants. Dans le chapitre I, la durabilité des solvants alternatifs sera discutée et des outils permettant de prédire les propriétés des solvants seront introduits.Dans le contexte de l'économie circulaire et du recyclage des déchets, les sous-produits sont désormais considérés comme une source alternative de composés naturels. Dans le chapitre II de ce travail, la valorisation des kiwis rejetés est proposée par l'extraction de composés bioactifs à l'aide de solvants durables à savoir des solvants eutectiques profonds (DES). Les résultats montrent que les extraits d'écorces de kiwi obtenus avec des DES à base d'acides carboxyliques présentent une activité antioxydante améliorée par rapport aux solvants conventionnels.Dans le domaine des industries de la parfumerie ou de l'agroalimentaire, les techniques d'extractions actuellement utilisées présentent plusieurs inconvénients. Dans le chapitre III de ce travail, des techniques alternatives ont été étudiées pour proposer de nouveaux ingrédients parfumés obtenus à l'aide de solvants durables. Des extraits de feuilles et de fruits de poivre rose (Schinus molle L.) ont été obtenus par extraction solide-liquide et hydrodistillation dans des solutions aqueuses de DES ou d'IL, tandis que les extraits de pétales de Rosa centifolia ont été obtenus par extraction solide-liquide dans des BioSol, DES et IL.Après extraction des plantes, les extraits naturels obtenus sont des mélanges chimiques complexes. Certaines applications nécessitant l'utilisation de composés purs, plusieurs techniques de séparation ont été développées. La chromatographie de partage centrifuge (CPC) est une technique de séparation utilisant les deux phases d'un système biphasique comme phase mobile et stationnaire pour effectuer des séparations chromatographiques préparatives. La possibilité d'utiliser des solvants durables et en particulier le DES pour former des systèmes biphasiques pour le CPC a été peu étudiée. Dans le chapitre IV de ce travail, le développement de systèmes biphasiques contenant du DES ont été étudiés comme systèmes potentiels de séparation des composés naturels. Enfin, le potentiel du modèle COSMO-RS dans la conception de systèmes biphasiques pour la séparation de composés naturels a été étudié. Les résultats démontrent que COSMO-RS prédit dans la plupart des cas les courbes binodales des systèmes biphasiques et les coefficients de partage des composés naturels avec une bonne précision. Ainsi, ces résultats indiquent que COSMO-RS peut être un outil puissant dans la conception de systèmes de séparation et de purification.Dans l'ensemble, ces travaux donnent un aperçu du potentiel de divers solvants durables pour l'extraction et la séparation de composés naturels
Natural plant extracts are valuable ingredients for a wide range of applications, particularly in the cosmetic or pharmaceutical industries or in the perfume or food industries. But the extraction of these natural compounds remains mainly carried out using volatile organic solvents (VOCs) and processes with significant environmental impacts. In the recent context of green chemistry and eco-extraction, sustainable alternative solvents have been developed to replace VOCs. Among these solvents, biobased solvents (BioSol), deep eutectic solvents (DES) and ionic liquids (ILs) have been the subject of intense studies over the last two decades. However, current developments in plant extraction techniques are mainly based on experimental trials, which limits the number of extraction conditions and solvents that can be evaluated. To address this limitation, several modeling tools have been developed to predict solvent properties and support solvent choice. In Chapter I, the sustainability of alternative solvents will be discussed and tools to predict solvent properties will be introduced.In the context of the circular economy and waste recycling, by-products are now considered as an alternative source of natural compounds. In chapter II of this work, the valorization of rejected kiwifruit is proposed by the extraction of bioactive compounds using sustainable solvents, namely deep eutectic solvents (DES). The results show that kiwi peel extracts obtained with carboxylic acid-based DES exhibit improved antioxidant activity compared to conventional solvents.In the field of perfumery or food industries, the extraction techniques currently used have several drawbacks. In chapter III of this work, alternative techniques were studied to propose new fragrance ingredients obtained using sustainable solvents. Extracts of leaves and fruits of pink pepper (Schinus molecular L.) were obtained by solid-liquid extraction and hydrodistillation in aqueous solutions of DES or IL, while extracts of petals of Rosa centifolia were obtained by solid-liquid extraction in BioSol, DES and IL.After extraction from the plants, the natural extracts obtained are complex chemical mixtures. Certain applications requiring the use of pure compounds, several separation techniques have been developed. Centrifugal partition chromatography (CPC) is a separation technique using the two phases of a biphasic system as mobile and stationary phase to perform preparative chromatographic separations. The possibility of using sustainable solvents and in particular DES to form biphasic systems for CPC has been little studied. In Chapter IV of this work, the development of biphasic systems containing DES were investigated as potential systems for separating natural compounds. Finally, the potential of the COSMO-RS model in the design of two-phase systems for the separation of natural compounds was investigated. The results demonstrate that COSMO-RS predicts in most cases the binodal curves of biphasic systems and the partition coefficients of natural compounds with good accuracy. Thus, these results indicate that COSMO-RS can be a powerful tool in the design of separation and purification systems.Overall, this work provides insight into the potential of various sustainable solvents for the extraction and separation of natural compounds

Solvation-thermodynamics models based on computational quantum mechanics, such as the conductor-like screening model (COSMO), provide a good alternative to traditional group-contribution methods for predicting thermodynamic phase behavior. Two COSMO-based thermodynamic models are COSMO-RS (real solvents) and COSMO-SAC (segment activity coefficient). The main molecule-specific input for these models is the sigma profile, or the probability distribution of a molecular surface segment having a specific charge density. Generating the sigma profiles represents the most time-consuming and computationally expensive aspect of using COSMO-based methods. A growing number of scientists and engineers are interested in the COSMO-based thermodynamic models, but are intimidated by the complexity of generating the sigma profiles. This thesis presents the first free, open-literature database of 1,513 self-consistent sigma profiles, together with two validation examples. The offer of these profiles will enable interested scientists and engineers to use the quantum-mechanics-based, COSMO methods without having to do quantum mechanics. This thesis summarizes the application experiences reported up to October 2004 to guide the use of the COSMO-based methods. Finally, this thesis also provides a FORTRAN program and a procedure to generate additional sigma profiles consistent with those presented here, as well as a FORTRAN program to generate binary phase-equilibrium predictions using the COSMO-SAC model.
Master of Science