The in situ measurement of solution supersaturation associated with the batch cooling crystallization of l-glutamic acid (LGA) at 500 mL and 20 L scale sizes is assessed via ATR-FTIR spectroscopy. A partial least squares chemometric calibration model was developed for the online prediction of LGA concentration from measured FTIR absorbance spectra overcoming some significant challenges related to the low sensitivity of LGA in the mid-IR frequency range, its low solubility in water, and its complex speciation chemistry. The solubility data of LGA in water over the temperature range from 40 to 80 °C, using ATR-FTIR, reveals excellent agreement with those obtained both from using a gravimetric method and literature data. The metastable zone width determined using the turbidimetric methods as a function of heating/cooling rates and solute concentration is found to increase with increasing cooling rate while it decreases with increasing solution concentration. Monitoring online crystallization via both spontaneous and seeded in 500 mL and 20 L crystallizers reveals good concentration predictions for seeded crystallization, while fouling of the ATR crystal prevents its routine use for unseeded crystallization studies. Higher supersaturation levels are found for the larger crystallizer scale-size consistent with enhancement of secondary nucleation at the smaller scale-size.
Crystallization in solutions under steady cooling is considered in the case of instantaneous nucleation, in which all crystallites appear at once in the solution and grow in the absence of crystallites born subsequently. Expressions are obtained for the total crystallite volume as a function of the steadily increasing undercooling. These expressions are employed for determining the dependence of the relative critical undercooling u(c) for crystallization on the cooling rate q. The resulting u(c)(q) formula reveals the physical meaning of the parameters in the linear relationship, often reported experimentally, between u(c) and q in double logarithmic coordinates. The results obtained are also directly applicable to overall crystallization of melts at sufficiently small undercoolings.
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