An examination of the solution chemistry, nucleation kinetics, crystal morphology, and polymorphic behavior of aqueous phase batch crystallized L-isoleucine at the 250 mL scale size

Nornizar Anuar, Wan Ramli Wan Daud, Kevin J. Roberts, Siti Kartom Kamarudin, Siti Masrinda Tasirin

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

An examination of the aqueous solution solubility and batch crystallization kinetics of L-isoleucine at the 250 mL scale size under a poly- and isothermal process condition is presented. Solubility data determined are consistent with the existence of two L-isoleucine polymorphic forms, in which both forms have different solubility and they are enantiotropically related. These polymorphs (A and B) can be recovered at different cooling rates of cooling crystallization. Crystal characterization using optical microscopy, differential scanning calorimetry, X-ray powder diffraction, and Fourier transform IR microscopy confirm this polymorphic behavior. Polythermal crystallization kinetic studies revealed the crystallization temperature increases with cooling rate and solute concentration, which results in a decrease of the metastable zone width (MSZW) with a decreasing cooling/heating rate. The study also revealed that cooling rates affect the polymorph formation, where at cooling rates of 0.25-0.75 °C/min, form B is formed, while a more stable polymorph A can be recovered at a cooling rate of 0.10 °C/min. Isothermal studies showed that the range of nucleation rate is between 1.79 × 10-5 and 7.53 × 10-4 kg/(m3 min), and the interfacial surface free energy at high and low supersaturation system is 1.74 and 0.576 mJ/m2, respectively. For a high supersaturation system, the critical cluster radius r* is between 5-17 Å, associated with between 3-121 molecules (N*), and for a low supersaturation system, r * is between 3 and 14 A and N* is between 1 and 64. For a pH range of 5.1-6.3 and a temperature range between 10 and 80 °C, zwitterion species of L-isoleucine has remained as a dominating species in both solubility and crystallization studies. Thermodynamics properties generated from solubility data were also presented and discussed.

Original languageEnglish
Pages (from-to)2853-2862
Number of pages10
JournalCrystal Growth and Design
Volume9
Issue number6
DOIs
Publication statusPublished - 3 Jun 2009

Fingerprint

crystal morphology
Isoleucine
Nucleation
Solubility
examination
nucleation
chemistry
Supersaturation
Cooling
cooling
Crystals
Crystallization
Polymorphism
solubility
kinetics
crystallization
Crystallization kinetics
supersaturation
isothermal processes
Heating rate

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

@article{e9eb069207244cf99e08c45850c01b87,
title = "An examination of the solution chemistry, nucleation kinetics, crystal morphology, and polymorphic behavior of aqueous phase batch crystallized L-isoleucine at the 250 mL scale size",
abstract = "An examination of the aqueous solution solubility and batch crystallization kinetics of L-isoleucine at the 250 mL scale size under a poly- and isothermal process condition is presented. Solubility data determined are consistent with the existence of two L-isoleucine polymorphic forms, in which both forms have different solubility and they are enantiotropically related. These polymorphs (A and B) can be recovered at different cooling rates of cooling crystallization. Crystal characterization using optical microscopy, differential scanning calorimetry, X-ray powder diffraction, and Fourier transform IR microscopy confirm this polymorphic behavior. Polythermal crystallization kinetic studies revealed the crystallization temperature increases with cooling rate and solute concentration, which results in a decrease of the metastable zone width (MSZW) with a decreasing cooling/heating rate. The study also revealed that cooling rates affect the polymorph formation, where at cooling rates of 0.25-0.75 °C/min, form B is formed, while a more stable polymorph A can be recovered at a cooling rate of 0.10 °C/min. Isothermal studies showed that the range of nucleation rate is between 1.79 × 10-5 and 7.53 × 10-4 kg/(m3 min), and the interfacial surface free energy at high and low supersaturation system is 1.74 and 0.576 mJ/m2, respectively. For a high supersaturation system, the critical cluster radius r* is between 5-17 {\AA}, associated with between 3-121 molecules (N*), and for a low supersaturation system, r * is between 3 and 14 A and N* is between 1 and 64. For a pH range of 5.1-6.3 and a temperature range between 10 and 80 °C, zwitterion species of L-isoleucine has remained as a dominating species in both solubility and crystallization studies. Thermodynamics properties generated from solubility data were also presented and discussed.",
author = "Nornizar Anuar and {Wan Daud}, {Wan Ramli} and Roberts, {Kevin J.} and Kamarudin, {Siti Kartom} and Tasirin, {Siti Masrinda}",
year = "2009",
month = "6",
day = "3",
doi = "10.1021/cg900133t",
language = "English",
volume = "9",
pages = "2853--2862",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - An examination of the solution chemistry, nucleation kinetics, crystal morphology, and polymorphic behavior of aqueous phase batch crystallized L-isoleucine at the 250 mL scale size

AU - Anuar, Nornizar

AU - Wan Daud, Wan Ramli

AU - Roberts, Kevin J.

AU - Kamarudin, Siti Kartom

AU - Tasirin, Siti Masrinda

PY - 2009/6/3

Y1 - 2009/6/3

N2 - An examination of the aqueous solution solubility and batch crystallization kinetics of L-isoleucine at the 250 mL scale size under a poly- and isothermal process condition is presented. Solubility data determined are consistent with the existence of two L-isoleucine polymorphic forms, in which both forms have different solubility and they are enantiotropically related. These polymorphs (A and B) can be recovered at different cooling rates of cooling crystallization. Crystal characterization using optical microscopy, differential scanning calorimetry, X-ray powder diffraction, and Fourier transform IR microscopy confirm this polymorphic behavior. Polythermal crystallization kinetic studies revealed the crystallization temperature increases with cooling rate and solute concentration, which results in a decrease of the metastable zone width (MSZW) with a decreasing cooling/heating rate. The study also revealed that cooling rates affect the polymorph formation, where at cooling rates of 0.25-0.75 °C/min, form B is formed, while a more stable polymorph A can be recovered at a cooling rate of 0.10 °C/min. Isothermal studies showed that the range of nucleation rate is between 1.79 × 10-5 and 7.53 × 10-4 kg/(m3 min), and the interfacial surface free energy at high and low supersaturation system is 1.74 and 0.576 mJ/m2, respectively. For a high supersaturation system, the critical cluster radius r* is between 5-17 Å, associated with between 3-121 molecules (N*), and for a low supersaturation system, r * is between 3 and 14 A and N* is between 1 and 64. For a pH range of 5.1-6.3 and a temperature range between 10 and 80 °C, zwitterion species of L-isoleucine has remained as a dominating species in both solubility and crystallization studies. Thermodynamics properties generated from solubility data were also presented and discussed.

AB - An examination of the aqueous solution solubility and batch crystallization kinetics of L-isoleucine at the 250 mL scale size under a poly- and isothermal process condition is presented. Solubility data determined are consistent with the existence of two L-isoleucine polymorphic forms, in which both forms have different solubility and they are enantiotropically related. These polymorphs (A and B) can be recovered at different cooling rates of cooling crystallization. Crystal characterization using optical microscopy, differential scanning calorimetry, X-ray powder diffraction, and Fourier transform IR microscopy confirm this polymorphic behavior. Polythermal crystallization kinetic studies revealed the crystallization temperature increases with cooling rate and solute concentration, which results in a decrease of the metastable zone width (MSZW) with a decreasing cooling/heating rate. The study also revealed that cooling rates affect the polymorph formation, where at cooling rates of 0.25-0.75 °C/min, form B is formed, while a more stable polymorph A can be recovered at a cooling rate of 0.10 °C/min. Isothermal studies showed that the range of nucleation rate is between 1.79 × 10-5 and 7.53 × 10-4 kg/(m3 min), and the interfacial surface free energy at high and low supersaturation system is 1.74 and 0.576 mJ/m2, respectively. For a high supersaturation system, the critical cluster radius r* is between 5-17 Å, associated with between 3-121 molecules (N*), and for a low supersaturation system, r * is between 3 and 14 A and N* is between 1 and 64. For a pH range of 5.1-6.3 and a temperature range between 10 and 80 °C, zwitterion species of L-isoleucine has remained as a dominating species in both solubility and crystallization studies. Thermodynamics properties generated from solubility data were also presented and discussed.

UR - http://www.scopus.com/inward/record.url?scp=66849106214&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=66849106214&partnerID=8YFLogxK

U2 - 10.1021/cg900133t

DO - 10.1021/cg900133t

M3 - Article

VL - 9

SP - 2853

EP - 2862

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 6

ER -