Solubility and Nucleation of Methyl Stearate as a Function of Crystallization Environment

Camacho, Diana M.; More, Iain; Lewtas, Ken

doi:10.1021/acs.energyfuels.7b03212

Cited by 11 publications

(11 citation statements)

References 41 publications

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“…17 Given the lack of studies on the crystallization of saturated methyl esters, it is the aim of this study to deliver fundamental information on the morphology and crystal growth kinetics of methyl stearate as a function of solution environment. These findings are complemented and cross-correlated in section 3.3 with unpublished results, 29 where a fundamental analysis of methyl stearate nucleation was carried out.…”

Section: Introductionmentioning

confidence: 64%

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Morphology and Growth of Methyl Stearate as a Function of Crystallization Environment

Camacho

Roberts

Muller

et al. 2016

Crystal Growth & Design

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In situ studies of methyl stearate growing from supersaturated n-dodecane, kerosene, and toluene solutions reveal strong evidence that solvent choice influences the crystal morphology and crystal growth kinetics. Crystals with similar habit are observed in all solvents, with the exception of lower supersaturations in kerosene, where a less symmetric morphology was observed. BFDH analysis based on the monoclinic C2 crystal structure of methyl stearate yielded the morphological indexation to be (110), (1–10), (−110), and (−1–10) for the dominant observed habit and (110) (1–10) (−1–10) (−240) (−3–10) for the less symmetric habit observed in kerosene solvent. Measurements of the growth rate for the (110) and (1–10) faces are similar for all solutions ranging from 0.02 to 1.13 μm/s, for significantly lower values of supersaturation in the case of toluene. The tendency of the growth rate dependence on σ was consistent with the Burton-Cabrera-Frank (BCF) growth mechanism in n-dodecane, the Birth and Spread (B&S) mechanism in kerosene and diffusion controlled in toluene solvent.

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Section: Introductionmentioning

confidence: 64%

“…Table presents an overview of results together with those obtained from the assessment of nucleation in the same solutions’ systems …”

Section: Resultsmentioning

confidence: 99%

Morphology and Growth of Methyl Stearate as a Function of Crystallization Environment

Camacho

Roberts

Muller

et al. 2016

Crystal Growth & Design

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“…In the current work, the PTFE-coated stirrer bar was cylindrical and had a length of 7 mm and a diameter of 2 mm. This equipment is designed for and has been used extensively for induction time, metastable zone width (through measurement of the onset of nucleation), and solubility (through measurement of the clear point) measurements in the literature. ,,− …”

Section: Experimental Sectionmentioning

confidence: 99%

“…Recently, the group of Davey has shown that shear has an effect on primary nucleation which limits the ability of some commonly used prediction methods to estimate primary nucleation rates in industrial crystallizers. Moreover, indirect measurements and mathematical models relating nucleation rate with induction times or metastable zone widths have also been developed by the group of Nyvlt, Kubota, and Kashchiev (KBHR model) under several theoretical assumptions.…”

Section: Introductionmentioning

confidence: 99%

Direct Measurements of Primary Nucleation Rates of p-Aminobenzoic Acid and Glutamic Acid and Comparison with Predictions from Induction Time Distributions

Cedeno

Maosoongnern

Flood

2018

Ind. Eng. Chem. Res.

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The model-based estimation of primary nucleation rates from the probability distribution of induction time measurements has been used extensively in the literature; however, there has been no experimental validation of this approach via direct measurements of nucleation rates. In this work, we compared the nucleation rates obtained from the probability distribution model against that measured from in situ optical reflectance measurement (ORM) with p-aminobenzoic acid and l-glutamic acid as model compounds. Results reveal that the primary nucleation rates obtained from stochastic models are several orders of magnitude lower than those measured from a direct particle-counting technique. Although differences in fluid dynamics due to agitation and crystallizer geometry may have an effect, this tremendous discrepancy provides strong evidence that primary nucleation rates obtained from induction time measurements are not scalable and should not be used for interpretation of nucleation rates in industrial applications.

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“…Based on this approach, it can be assessed whether the dissolution is enthalpy or entropy-driven [ 29 , 30 , 31 , 32 ]. Notably, the knowledge of entropic/enthalpic contributions to the Gibbs free energy, as well as activity coefficients in saturated solutions analysis, is of a particular importance in describing the crystallization process [ 33 , 34 ].…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Characteristics of Phenacetin in Solid State and Saturated Solutions in Several Neat and Binary Solvents

et al. 2021

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The thermodynamic properties of phenacetin in solid state and in saturated conditions in neat and binary solvents were characterized based on differential scanning calorimetry and spectroscopic solubility measurements. The temperature-related heat capacity values measured for both the solid and melt states were provided and used for precise determination of the values for ideal solubility, fusion thermodynamic functions, and activity coefficients in the studied solutions. Factors affecting the accuracy of these values were discussed in terms of various models of specific heat capacity difference for phenacetin in crystal and super-cooled liquid states. It was concluded that different properties have varying sensitivity in relation to the accuracy of heat capacity values. The values of temperature-related excess solubility in aqueous binary mixtures were interpreted using the Jouyban–Acree solubility equation for aqueous binary mixtures of methanol, DMSO, DMF, 1,4-dioxane, and acetonitrile. All binary solvent systems studied exhibited strong positive non-ideal deviations from an algebraic rule of mixing. Additionally, an interesting co-solvency phenomenon was observed with phenacetin solubility in aqueous mixtures with acetonitrile or 1,4-dioxane. The remaining three solvents acted as strong co-solvents.

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Solubility and Nucleation of Methyl Stearate as a Function of Crystallization Environment

Cited by 11 publications

References 41 publications

Morphology and Growth of Methyl Stearate as a Function of Crystallization Environment

Morphology and Growth of Methyl Stearate as a Function of Crystallization Environment

Direct Measurements of Primary Nucleation Rates of p-Aminobenzoic Acid and Glutamic Acid and Comparison with Predictions from Induction Time Distributions

Thermodynamic Characteristics of Phenacetin in Solid State and Saturated Solutions in Several Neat and Binary Solvents

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