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Solubility of Nifedipine and Lacidipine in Supercritical CO2: Measurement and Correlation

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Abstract

Solubilities of two calcium channel blockers, nifedipine and lacidipine, were measured in supercritical carbon dioxide at T = (313, 323, and 333) K over the pressure range (12.0–36.0) MPa using a dynamic-analytical apparatus. The solubility values obtained are in the range of (0.18–7.05) × 10−5 mol·mol−1. The solubilities of the two solids show similar trends with a crossover region of the respective isotherms in the range 18.0–21.0 MPa. The experimental solubility data were correlated with several different models. The semi-empirical density-based models provided satisfactory correlation results with AARD values lower than 10%. According to the results of the Méndez-Santiago and Teja models, the measured solid solubility data are quite consistent at all experimental conditions, which indicates the reliability of the data. The compressed gas model of the Peng–Robinson equation of state, combined with the two parameter van der Waals mixing rule (PR-EoS-VDW2) model, gives better correlation results than the PR-EoS-VDW1 model. The expanded liquid model based on Scatchard–Hildebrand regular solution theory can be used for solubility prediction, but the correlation results for nifedipine and lacidipine by the model are inferior to the compressed gas models in this work.

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Abbreviations

T :

Temperature (in K), Eq. 2

s :

Solubility of the solute (in kg·m−3), Eq. 2

p :

Pressure (in MPa), Eq. 3

p ref :

Reference pressure p ref = 0.1 MPa, Eq. 3

y 2 :

Mole fraction of the solute in supercritical solution (in mol·mol−1), Eq. 5

p sat2 :

The saturation pressure of the solute at the given temperature (in MPa), Eq. 5

\( v_{2}^{\text{s}} \) :

Molar volume of the solid solute (in cm3·mol−1), Eq. 5

R :

Gas constant R = 8.3145 J·mol−1·K−1, Eq. 5

a m :

Attraction parameter of the supercritical solution (in MPa·m3·mol−1), Eq. 6

b m :

Repulsion parameter of the supercritical solution (in cm3·mol−1), Eq. 7

a :

Attraction parameter (in MPa·m3·mol−1), Eq. 10

b :

Repulsion parameter (in cm3·mol−1), Eq. 10

v :

Molar volume of the supercritical phase (in cm3·mol−1), Eq. 10

\( f_{2}^{\text{s}} \) :

Solid solute fugacity (in MPa), Eq. 12

\( f_{2}^{\text{l}} \) :

Liquid solute fugacity (in MPa), Eq. 12

\( \Delta c_{\text{p}} \) :

Difference between the heat capacities of the liquid the solid solute (in J·mol−1), Eq. 12

\( \Delta H_{\text{m}} \) :

Enthalpy of fusion of solute (in J·mol−1), Eq. 13

T m :

Melting temperature of solute (in K), Eq. 13

\( v_{2}^{l} \) :

Liquid molar volume of solute (in cm3·mol−1), Eq. 15

\( v_{1} \) :

Molar volume of the sc-CO2 (cm3·mol−1), Eq. 16

\( y_{2}^{ \exp } \) :

Experimental solubility of the solute in sc-CO2 (in mol·mol−1), Eq. 19

\( y_{2}^{\text{cal}} \) :

Calculated solubility of the solute in sc-CO2 (in mol·mol−1), Eq. 19

N :

Number of solubility values, Eq. 19

W :

Mass of drug loaded in the extractor (in g), Eq. 20

F :

Mass flow rate of CO2 (in g·s−1), Eq. 20

ρ :

Density of sc-CO2 (in kg·m−3), Eq. 2

ρ ref :

Reference density ρ ref = 700 kg·m−3, Eq. 3

\( \varphi_{2}^{\text{sat}} \) :

Fugacity coefficient of the pure solute at the saturation pressure, Eq. 5

\( \varphi_{2} \) :

Fugacity coefficient of the solute in the supercritical phase under the experimental conditions (p, T), Eq. 5

γ 2 :

The solute activity coefficient in the supercritical phase under the experimental condition (p, T), Eq. 12

\( \delta_{1} \) :

Solubility parameter of sc-CO2 (in MPa0.5), Eq. 15

\( \delta_{2} \) :

Solubility parameter of the solute (in MPa0.5), Eq. 15

\( \phi_{1} \) :

Volume fraction of the solvent, Eq. 15

\( \tau \) :

Contact time (in s), Eq. 20

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Acknowledgement

This work was supported by the National Natural Science Foundation of China (21106107, 21206077).

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Authors and Affiliations

  1. Key Laboratory of Organic Solar Cells and Photochemical Conversion, School of Chemistry & Chemical Engineering, Tianjin University of Technology, Tianjin, 300384, People’s Republic of China

    Yanlou Wang, Tiantian Meng, Dongdong Jia, Yongyue Sun & Naixuan Li

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  1. Yanlou Wang
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Correspondence to Dongdong Jia.

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Wang, Y., Meng, T., Jia, D. et al. Solubility of Nifedipine and Lacidipine in Supercritical CO2: Measurement and Correlation. J Solution Chem 46, 70–88 (2017). https://doi.org/10.1007/s10953-016-0550-2

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