Thermodynamics of fenoxycarb in solution

Kuhs, Manuel; Svärd, Michael; Rasmuson, Åke C.

doi:10.1016/j.jct.2013.06.007

Cited by 18 publications

(23 citation statements)

References 20 publications

(28 reference statements)

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“…13 It was dissolved for 24 hours in a sealed 1 L vessel with a large magnetic stir bar spinning at 400 rpm, and the vessel submersed in a 25 °C water bath (Grant GR150, stability ± 0.005 °C and uniformity ± 0.02 °C at 36.85 °C). 20 mL portions were aliquoted into 29 glass vials (30mL) using pre-heated syringes (20 mL) equipped with 0.2 µm PTFE filters.…”

Section: Methodsmentioning

confidence: 99%

“…According to published solubility data, this gives a superstation ratio of 4.33 (expressed as c/c*, where c is the actual concentration in mass fenoxcarb per mass isopropanol, and c* the equilibrium concentration at 5 °C). 13 This initial set of induction times will be referred to as "first nucleation", the procedure being almost identical to that used by Nordström et al to demonstrate solution history effects on polymorphism. 9 The time to reach a temperature deviating by 1 °C from the final value was measured to be approximately 1 minute (Dostmann P750 with Pt100 immersion probe, accuracy 0.03 °C).…”

Section: Methodsmentioning

confidence: 99%

“…Fenoxycarb is highly soluble in isopropanol, exhibiting a solute-to-solvent molar ratio of 0.058 mole/mole in solution saturated at 20 °C, 13 i.e. for each fenoxycarb molecule there are only 17 molecules of isopropanol.…”

Section: Computational Molecular Level Analysismentioning

confidence: 99%

See 2 more Smart Citations

Influence of History of Solution in Crystal Nucleation of Fenoxycarb: Kinetics and Mechanisms

Kuhs

Żegliński

Rasmuson

2014

Crystal Growth & Design

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Nearly 1800 induction time experiments have been performed on crystal nucleation of fenoxycarb in isopropanol to investigate the influence of solution pretreatment. For each preheating temperature and preheating time, at least 80 experiments were performed to obtain statistically valid results. The relationship between the inverse of the induction time and the preheating time can be reasonably described as an exponential decay having time constants ranging up to days depending on the temperature. This dependence on the preheating temperature corresponds to an activation energy of over 200 kJ/mol. Given sufficiently long preheating time and high temperature, the solution appears to reach a steady-state where the "memory" effect has disappeared. Density functional theory modelling suggests that the molecular packing in the crystal lattice is not the thermodynamically stable configuration at the level of simple dimers in solution, while modelling of the first solvation shell reveals that solute aggregation must exist in solution due to the low solvent to solute molecular ratio. It is thus hypothesized that the dissolution of crystalline material at first leaves molecular assemblies in solution that retain features of the crystalline structure which facilitates subsequent nucleation. However, the longer the solution is kept at a temperature above the saturation temperature and the higher the temperature, the more these assemblies disintegrate, and transform into molecular structures less suited to form critical nuclei..

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Influence of History of Solution in Crystal Nucleation of Fenoxycarb: Kinetics and Mechanisms

Kuhs

Żegliński

Rasmuson

2014

Crystal Growth & Design

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“…However, linearity in a van't Hoff plot is not to be expected, [10] and when it is occasionally observed it is the result of a cancelling out of the temperature dependences of the enthalpy of fusion of the pure solid and the solution activity coefficient. [11] The van't Hoff curves of the solubility of FII in all investigated solvents are visibly non-linear.…”

Section: Solubility Of Fii In Pure Organic Solventsmentioning

confidence: 95%

“…(11) and the coefficients in Table 3. In all solvents at all investigated temperatures, the activity coefficient at saturation is well above unity.…”

Section: Solubility Of Fii In Pure Organic Solventsmentioning

confidence: 99%

Thermodynamic Stability Analysis of Tolbutamide Polymorphs and Solubility in Organic Solvents

Svärd

Valavi

Khamar

et al. 2016

Journal of Pharmaceutical Sciences

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Melting temperatures and enthalpies of fusion have been determined by differential scanning calorimetry (DSC) for two polymorphs of the drug tolbutamide: FI H and FV. Heat capacities have been determined by temperature-modulated DSC for four polymorphs: FI L , FI H , FII, FV, and for the supercooled melt. The enthalpy of fusion of FII at its melting point has been estimated from the enthalpy of transition of FII into FI H through a thermodynamic cycle. Calorimetric data has been used to derive a quantitative polymorphic stability relationship between these four polymorphs, showing that FII is the stable polymorph below approx. 333 K, above which temperature FI H is the stable form up to its melting point. The relative stability of FV is well below the other polymorphs. The previously reported kinetic reversibility of the transformation between FI L and FI H has been verified using in situ Raman spectroscopy. The solid-liquid solubility of FII has been gravimetrically determined in five pure organic solvents (methanol, 1-propanol, ethyl acetate, acetonitrile and toluene) over the temperature range 278 K -323 K. The ideal solubility has been estimated from calorimetric data, and solution activity coefficients at saturation in the five solvents determined. All solutions show positive deviation from Raoult's law, and all van't Hoff plots of solubility data are non-linear. The solubility in toluene is well below that observed in the other investigated solvents. Solubility data has been correlated and extrapolated to the melting point using a semiempirical regression model.

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(Solid+liquid) solubility of organic compounds in organic solvents – Correlation and extrapolation

Svärd

Rasmuson

2014

The Journal of Chemical Thermodynamics

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A semi-empirical model is developed for the regression of solid-liquid solubility data with temperature. The model fulfils the required boundary conditions, allowing for robust extrapolation to higher and lower temperatures. The model combines a representation of the solid-state activity which accommodates a temperature-dependent heat capacity difference contribution with a scaled three-parameter Weibull function representing the temperature dependence of the solution activity coefficient at equilibrium. Evaluation of the model is based on previously published experimental calorimetric and solubility data of four organic compounds, fenoxycarb, fenofibrate, risperidone and butyl paraben, in five common organic solvents, methanol, ethyl acetate, acetone, acetonitrile, and toluene. The temperature dependence of the van't Hoff enthalpy of solution and its components is analysed and discussed. Among the four compounds the influence of temperature on the enthalpy of fusion varies from moderate to substantial. Based on the semi-empirical model, a new equation containing three adjustable parameters is proposed for regression and extrapolation of solubility data for cases when only melting data and solubility data is available. The equation is shown to provide good accuracy and robustness when evaluated against the full semiempirical model as well as against commonly used, more simple empirical equations. It is shown how such a model can be used to obtain an estimate of the heat capacity difference for cases where accurate solubility data is available in multiple solvents.2

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Thermodynamics of fenoxycarb in solution

Cited by 18 publications

References 20 publications

Influence of History of Solution in Crystal Nucleation of Fenoxycarb: Kinetics and Mechanisms

Influence of History of Solution in Crystal Nucleation of Fenoxycarb: Kinetics and Mechanisms

Thermodynamic Stability Analysis of Tolbutamide Polymorphs and Solubility in Organic Solvents

(Solid+liquid) solubility of organic compounds in organic solvents – Correlation and extrapolation

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