Effects of Ultrasound and Its Amplitude on the Metastable Zone Width, Induction Time, and Nucleation Kinetics of Pyrazinamide in Acetone

Abstract

A systematic investigation is carried out to analyze the effect of ultrasonic amplitudes (10, 30, and 50%) on the metastable zone width (MSZW) and induction time (t ind ) for unseeded batch cooling crystallization of pyrazinamide from its acetone solution. The MSZW is measured at five different saturation temperatures (293.15, 298.15, 303.15, 308.15, and 313.15 K) with different cooling rates. Five cooling rates (30, 24, 18, 12, and 6 K/h) were selected for the silent case, and three cooling rates (24, 18, and 6 K/h) were selected for sonicated cases with three different ultrasonic amplitudes (10, 30, and 50%). The induction time is measured at five different supersaturation ratios (1.05, 1.10, 1.15, 1.20, and 1.25) at three different saturation temperatures (293.15, 303.15, and 313.15 K) for both silent and sonicated cases. For the silent cases, at a given saturation temperature, the MSZW increases by 63−73% with increase in cooling rate from 6 to 30 K/h. Again, at a given cooling rate, the MSZW decreases by 19−40% with increase in saturation temperature from 293.15 to 313.15 K. For sonicated cases, at a given saturation temperature and cooling rate, the MSZW is decreased by almost half at a higher ultrasonic amplitude (50%). The MSZW data are analyzed using four different approaches (Nyvlt's approach, Kubuto's approach, Sangwal's self-consistent Nyvlt-like equation approach, and Sangwal's classical three-dimensional nucleation theory approach) to calculate various nucleation parameters. The application of ultrasound reduces the apparent nucleation order significantly, and the nucleation rate was increased by 2−3 times compared to the silent cases with increasing ultrasonic amplitude. The data obtained from the induction time are analyzed using classical nucleation theory to calculate important nucleation parameters such as interfacial energy (1.05−1.29 mJ/m 2 ) and various nucleation parameters such as nucleation rate (5.23 × 10 22 −7.28 × 10 25 #/m 3 s), critical radius (0.34−1.91 Å), and critical free energy (0.05 × 10 20 −1.91 × 10 20 J). Furthermore, the concept of nucleation potential is used to estimate MSZW from the measured induction time data. The estimated values are seen to be 80−85% accurate at low saturation temperatures and 66−72% accurate at higher saturation temperatures for the pyrazinamide−acetone solution.

Uncovering the Solvent–Solute Interaction Mechanism in Nucleation of Erythritol Based on Metastable Zone Widths: Experimental Kinetics and Molecular Dynamics Simulations

“…The interfacial energy was calculated via the induction time data based on CNT, and then compared with the results of PTM to verify the dependability of the experimental data. The extrapolated MSZW of Pyrazinamide in acetone from induction time data via concept of nucleation potential was reliable for lower saturation temperatures . Even in an electrolyte system, the estimated MSZWs also showed improved accuracies and a tendency to be positively correlated with both the supersaturation temperature and cooling rate .…”

Enhanced Direct Crystallization Resolution of Racemates Mediated in Chiral Ionic Liquid Cosolvent Mixtures: Experimental, Statistical, and QM Simulation Studies

“…The induction period ( t ind ), a crucial kinetic parameter, was employed to investigate the selective interactions between chiral solvents and solutes . The determination of t ind of Thr enantiomeric crystals in water and CCM-0.3 was performed by a laser method at 283.15 K, respectively.…”

“…The induction period (t ind ), a crucial kinetic parameter, was employed to investigate the selective interactions between chiral solvents and solutes. 34 The determination of t ind of Thr enantiomeric crystals in water and CCM-0.3 was performed by a laser method at 283.15 K, respectively. First, saturated solutions of Thr enantiomers in water and CCM-0.3 were prepared at seven temperatures higher than 283.15 K, respectively.…”

Metastable Zone Width and Primary Nucleation Kinetics for Crystallization of KCl from a KCl-MgCl2-H2O System

“…18 Maharana and Sarkar investigated the effect of ultrasound on the metastable zone width of pyrazinamide from acetone solution and found that application of ultrasound increased the nucleation rate constant by 2-to 3-fold. 21 Zhao et al measured the metastable zone width of nicotinic acid in ethanol and revealed that temperature and driving force jointly affect the metastable zone width and nucleation rate. 28 Cao et al studied the nucleation behavior of isosorbide 5-mononitrate by metastable zone width, during which the Nyvlt's equation and modified Sangwal's theory were employed to obtain nucleation kinetic parameters.…”