Solubility of celecoxib in N-methyl-2-pyrrolidone+water mixtures at various temperatures: Experimental data and thermodynamic analysis

Sarah Nozohouri,Ali Shayanfar,Zaira Johanna Cárdenas,Fleming Martinez,Abolghasem Jouyban 한국화학공학회 2017 Korean Journal of Chemical Engineering Vol.34 No.5

Solubility is one of the most significant physicochemical properties of drugs, and improving the solubility of drugs is still a challenging subject in pharmaceutical sciences due to requirements of enhancing their bioavailability. Celecoxib, according to the biopharmaceutics classification system (BCS), is a class 2 drug, possessing low water solubility (<5 μg·mL−1) and high permeability. Increasing the solubility of this group can lead to improved bioavailability, dose reduction and subsequently, increased efficiency and reduced side effects. In this study, celecoxib solubility was determined in binary mixtures of N-methyl-2-pyrrolidone (NMP)+water at 293.2, 298.2, 303.2, 308.2 and 313.2 K. The solubility of celecoxib is increased with the addition of NMP to the aqueous solutions and reaches a maximum value in neat NMP. In addition, increased temperature leads to enhanced solubility of celecoxib in a given solvent composition. The solubility data of celecoxib in NMP+water at different temperatures were correlated using different mathematical models including, the Jouyban-Acree model and a combination of the Jouyban-Acree and van’t Hoff models. Thermodynamic parameters, Gibbs energy, enthalpy and entropy of dissolution processes were performed based on Gibbs and van’t Hoff equations. Thermodynamic analysis allowed observing two main entropy or enthalpy-driven dissolution mechanisms, varying according to the composition of aqueous mixtures. Moreover, preferential solvation of celecoxib by water is observed in water-rich mixtures but preferential solvation by NMP was seen in mixtures with similar composition and also in NMP-rich mixtures.

Evaluation and Comparison of the Solubility Models for Solute in Monosolvents

Min-jie Zhi,Wan-feng Chen,Yang-bo Xi 한국화학공학회 2024 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.62 No.1

The solubility of Cloxacillin sodium in ethanol, 1-propanol, isopropanol, and acetone solutions was measured at different temperatures. The melting property was also tested by using a differential scanning calorimeter (DSC). Then, the solubility data were fitted using Apelblat equation and λh equation, respectively. The Wilson model and NRTL model were not utilized to correlate the test data, since Cloxacillin sodium will decompose directly after melting. For comparison purposes, the four empirical models, i.e., Apelblat equation, λh equation, Wilson model and NRTL Model, were evaluated by using 1155 solubility curves of 103 solutes tested under different monosolvents and temperatures. The comparison results indicate that the Apelblat equation is superior to the others. Furthermore, a new method (named the calculation method) for determining the Apelblat equation using only three data points was proposed to solve the problem that there may not be enough solute in the determination of solubility. The log-logistic distribution function was used to further capture the trend of the correlation and to make better quantitative comparison between predicted data and the experimental ones for the Apelblat equation determined by different methods (fitting method or calculation method). It is found that the proposed calculation method not only greatly reduces the number of test data points, but also has satisfactory prediction accuracy.

A modified non-equilibrium lattice fluid model based on corrected fractional free volume of polymers for gas solubility prediction

Abolfazl Jomekian,Bahamin Bazooyar,Seyed Jalil Poormohammadian,Parviz Darvishi 한국화학공학회 2019 Korean Journal of Chemical Engineering Vol.36 No.12

We propose a model based on non-equilibrium lattice fluid (NELF) theory and corrected fractional free volume of polymers to effectively and accurately predict the solubility of gases in different polymers. The method to achieve this purpose is based on the utilization of NELF model infinite dilution solubility coefficient (S0) as the base of predictive calculations. To account for the isolated pore in the polymer matrix in density estimation, a fractional free volume correction factor (β) was introduced in NELF model. The modified NELF model was successfully applied for prediction of solubility of C3H8 and CO2 in polyethylene oxide (PEO) and CO2 in polyethylene terephthalate (PET), isotactic polypropylene (i-PP), polyetherimide (PEI), polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) with adjustments in β value and depth of diffusion of gases in polymer matrix (ζ) at different pressures and temperatures. This work involves multi-objective optimization using genetic algorithm of MATLAB toolbox with adjusted settings. It applies to find the optimum temperature at which the minimum standard deviation of β for different gas-polymer systems is obtained. β showed the same trend of change with temperature as the constrained pressure imposed on the amorphous phase in semi-crystalline polymers. A cubic correlation for standard deviation for β versus temperature was obtained which was able to anticipate the changing trend of β at different temperatures. The chisquare test results verified that compared with original NELF model, a more accurate model for prediction of gas solubilities in polymers has been proposed.

EFFECT OF CARBONATE ON THE SOLUBILITY OFNEPTUNIUM IN NATURAL GRANITIC GROUNDWATER

김봉영,J. Y. OH,백민훈,윤종일 한국원자력학회 2010 Nuclear Engineering and Technology Vol.42 No.5

This study investigates the solubility of neptunium (Np) in the deep natural groundwater of the Korea Atomic EnergyResearch Institute Underground Research Tunnel (KURT). According to a Pourbaix diagram (pH-Ehdiagram) that wascalculated using the geochemical modeling program PHREEQC 2.0, the redox potential and the carbonate ion concentrationboth control the solubility of neptunium. The carbonate effect becomes pronounced when the total carbonate concentration ishigher than 1.5×10-2M at Eh= -200 mV and the pH value is 10. Given the assumption that the solubility-limiting stablesolid phase is Np(OH)4(am) under the reducing condition relevant to KURT, the soluble neptunium concentrations were inthe range of 1×10-9M to 3×10-9M under natural groundwater conditions. However, the solubility of neptunium, which wascalculated with the formation constants of neptunium complexes selected in an OECD-NEA TDB review, strongly deviatesfrom the value measured in natural groundwater. Thus, it is highly recommended that a prediction of neptunium solubility isbased on the formation constants of ternary Np(IV) hydroxo-carbonato complexes, even though the presence of thosecomplexes is deficient in terms of the characterization of neptunium species. Based on a comparison of the measurementsand calculations of geochemical modeling, the formation constants for the “upper limit” of the Np(IV) hydroxo-carbonatocomplexes, namely Np(OH)y(CO3)z4-y-2z, were appraised as follows: log Kο122= -3.0±0.5 for Np(OH)2(CO3)22-, log Kο131=-5.0±0.5 for Np(OH)3(CO3)-, and log Ko141= -6.0±0.5 for Np(OH)4(CO3)

Hybrid neural network for prediction of CO2 solubility in monoethanolamine and diethanolamine solutions

Mohamed Kheireddine Aroua,Mohd Azlan Hussain,Chun-Yang Yin,Ramzalina Abd Rahman,Noor Asriah Ramli 한국화학공학회 2010 Korean Journal of Chemical Engineering Vol.27 No.6

The solubility of CO2 in single monoethanolamine (MEA) and diethanolamine (DEA) solutions was predicted by a model developed based on the Kent-Eisenberg model in combination with a neural network. The combination forms a hybrid neural network (HNN) model. Activation functions used in this work were purelin, logsig and tansig. After training, testing and validation utilizing different numbers of hidden nodes, it was found that a neural network with a 3-15-1 configuration provided the best model to predict the deviation value of the loading input. The accuracy of data predicted by the HNN model was determined over a wide range of temperatures (0 to 120 oC), equilibrium CO2 partial pressures (0.01 to 6,895 kPa) and solution concentrations (0.5 to 5.0M). The HNN model could be used to accurately predict CO2 solubility in alkanolamine solutions since the predicted CO2 loading values from the model were in good agreement with experimental data.

EFFECT OF CARBONATE ON THE SOLUBILITY OF NEPTUNIUM IN NATURAL GRANITIC GROUNDWATER

Kim, B.Y.,Oh, J.Y.,Baik, M.H.,Yun, J.I. Korean Nuclear Society 2010 Nuclear Engineering and Technology Vol.42 No.5

This study investigates the solubility of neptunium (Np) in the deep natural groundwater of the Korea Atomic Energy Research Institute Underground Research Tunnel (KURT). According to a Pourbaix diagram (pH-$E_h$ diagram) that was calculated using the geochemical modeling program PHREEQC 2.0, the redox potential and the carbonate ion concentration both control the solubility of neptunium. The carbonate effect becomes pronounced when the total carbonate concentration is higher than $1.5\;{\times}\;10^{-2}$ M at $E_h$ = -200 mV and the pH value is 10. Given the assumption that the solubility-limiting stable solid phase is $Np(OH)_4(am)$ under the reducing condition relevant to KURT, the soluble neptunium concentrations were in the range of $1\;{\times}\;10^{-9}$ M to $3\;{\times}\;10^{-9}$ M under natural groundwater conditions. However, the solubility of neptunium, which was calculated with the formation constants of neptunium complexes selected in an OECD-NEA TDB review, strongly deviates from the value measured in natural groundwater. Thus, it is highly recommended that a prediction of neptunium solubility is based on the formation constants of ternary Np(IV) hydroxo-carbonato complexes, even though the presence of those complexes is deficient in terms of the characterization of neptunium species. Based on a comparison of the measurements and calculations of geochemical modeling, the formation constants for the "upper limit" of the Np(IV) hydroxo-carbonato complexes, namely $Np(OH)_y(CO_3)_z^{4-y-2z}$, were appraised as follows: log $K^{\circ}_{122}\;=\;-3.0{\pm}0.5$ for $Np(OH)_2(CO_3)_2^{2-}$, log $K^{\circ}_{131}\;=\;-5.0{\pm}0.5$ for $Np(OH)_3(CO_3)^-$, and log $K^{\circ}_{141}\;=\;-6.0{\pm}0.5$ for $Np(OH)_4(CO_3)^{2-}$.

Experimental Study and Correlation of the Solid-liquid Equilibrium of Some Amino Acids in Binary Organic Solvents

Adel Noubigh,Mustafa Jaipallah Abualreish 한국화학공학회 2024 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.62 No.2

Under ordinary atmospheric circumstances, the gravimetric technique was used to measure the solubility of L-cysteine (L-Cys) and L-alanine (L-Ala) in various solvents, including methyl alcohol, ethyl acetate, and mixtures of the two, in the range o 283.15 K to 323.15 K. Both individual solvents and their combinations showed a rise in the solubility of L-Cys and L-Ala with increasing temperature, according to the analyzed data but when analyzed at a constant temperature in the selected mixed solvents, the solubility declined with decreasing of initial mole fractions of methyl alcohol. To further assess, the relative utility of the four solubility models, we fitted the solubility data using the Jouyban-Acree (J-A), van’t Hoff-Jouyban-Acree (V-J-A), Apelblat-Jouyban-Acree (A-J-A), and Ma models followed by evaluation of the values of the RAD information criteria and the RMSD were. The dissolution was also found to be an entropy-driven spontaneous mixing process in the solvents since the thermodynamic parameters of the solvents were determined using the van't Hoff model. In order to support the industrial crystallization of L-cysteine and L-alanine and contribute to future theoretical research, we have determined the experimental solubility, correlation equations, and thermodynamic parameters of the selected amino acids during the dissolution process.

A comprehensive comparison among four different approaches for predicting the solubility of pharmaceutical solid compounds in supercritical carbon dioxide

Gholamhossein Sodeifian,Seyed Ali Sajadian,Fariba Razmimanesh,Nedasadat Saadati Ardestani 한국화학공학회 2018 Korean Journal of Chemical Engineering Vol.35 No.10

Supercritical technologies have been developed in the food, environmental, biochemical and pharmaceutical product processing during the recent decades. Obtaining accurate experimental solubilities of pharmaceutical compounds in supercritical carbon dioxide (SC-CO2) and their correlations are highly important and essential for the design of industrial operating units. In this study, the solubilities of six pharmaceutical compounds (Anti-HIV, Antiinflammatory and Anti-cancer) in SC-CO2 were correlated using four different models: cubic equation of state (EoS) model (SRK and modified-Pazuki EoSs), empirical and semi-empirical models (Chrastil, Mendez-Santiago-Teja, Spark et al. and Bian et al. models), regular solution model coupled with the Flory-Huggins equation, and an artificial neural network-based (ANN-based) model. In EoS calculations, twin-parametric van der Waals (vdW2) and Panagiotopoulos-Reid (mrPR) mixing rules were used for estimating the supercritical solution properties, with three different sets employed for obtaining critical and physicochemical properties of the solid compounds. To evaluate the capabilities of various approaches, a comprehensive comparison was carried out among the four models based on several statistical criteria, including AARD, Radj and F-value. Results of the analysis of variance (ANOVA) indicated that the ANN-based model provided the best results in terms of correlating the experimental solubility of the pharmaceutical compounds in SC-CO2.

Solubility and partial molar volume of N,N-dimethylformamide diethyl acetal in supercritical carbon dioxide: Measurement and correlations

Piyong Zhang,Hai-Jian Yang,Lingxiao Xu 한국공업화학회 2014 Journal of Industrial and Engineering Chemistry Vol.20 No.4

The solubilities of N,N-dimethylformamide diethyl acetal were measured at temperatures ranging from 313 to 353 K and pressures from 7.8 to 13.3 MPa in supercritical carbon dioxide. The measured solubility data were correlated using the Chrastil, Sung and Shim (SS), and Jouyban–Chan–Foster (JCF) semiempirical models. Consequently, the calculated results showed satisfactory agreement with experimental data and differed from the measured values by between 4.56 and 6.10%. The correlated results indicated that the JCF model provided the best fitness. Solubility data were also utilized to estimate the partial molar volume for the compound in the supercritical phase using the theory developed by Kumar and Johnston.

A practical approach for kinetic analysis of hydrogenation of complex mineral base oil

Modi Siddharth,Tiwari Anand Kumar,Rao Meka Srinivasa,Snigdha Thummalapalli,Saritha Thummalapalli,Gupta Thummalapalli Chandra Sekhara Manik,Kumar Ajay 한국화학공학회 2023 Korean Journal of Chemical Engineering Vol.40 No.7

The mineral base oil contains paraffins, naphthenes and aromatic hydrocarbons (AH) with carbon chains ranging from C14 to C60. The presence of AH in base oil affects the performance of the product in many industrially oriented applications. The base oil considered in this work had AH around 14% w/w that needed to be reduced below 5% w/w for some applications and ideally 0% w/w. This paper demonstrates the practical approach for hydrogenation of complex mineral base oil for reducing AH. The mineral base oil rich in C20 was taken as the representative component. The hydrogen solubility in the oil was estimated using NRTL model. The semi-batch hydrogenation experiments were performed at different conditions and conversion of AH as high as 79% (i.e. 3% w/w) could be achieved. A second-order pseudo-homogeneous reaction kinetic model was proposed and validated. The conditions for reaction kinetics were optimized to achieve desirable conversion using Aspen Plus. To develop a continuous process for hydrogenation of AH, experiments were performed in a lab scale fixed bed reactor and the applicability of the kinetic model was validated. The kinetics was observed to be free of internal and external mass transfer limitations under lab scale conditions.