Crystal Growth of Salicylic Acid in Organic Solvents - ACS Publications

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Crystal Growth of Salicylic Acid in Organic Solvents Lijun Jia, Michael Svärd, and Åke C. Rasmuson Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01415 • Publication Date (Web): 06 Apr 2017 Downloaded from http://pubs.acs.org on April 10, 2017

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Crystal Growth & Design

Cover Page Crystal Growth of Salicylic Acid in Organic Solvents Lijun Jia 1, Michael Svärd 1,2, Åke C. Rasmuson * 1,2 1

Synthesis and Solid State Pharmaceutical Centre, Materials and Surface Science Institute, Department of Chemical and Environmental Science, University of Limerick, Limerick (Ireland) 2 Department of Chemical Engineering and Technology, KTH Royal Institute of Technology, SE-100 44 Stockholm (Sweden) *email: [email protected]

The crystal growth rate of salicylic acid has been determined by seeded isothermal desupersaturation experiments in different organic solvents (methanol, acetone, ethyl acetate and acetonitrile) and at different temperatures (10 °C, 15 °C, 20 °C and 25 °C). In situ ATRFTIR spectroscopy and principal component analysis (PCA) was employed for the determination of solution concentration. Activity coefficient ratios are approximately accounted for in the driving force determination. The results show that the dependence of the growth rate on the solvent at equal driving force varies with temperature, e.g. at 25 °C, the growth rate is highest in ethyl acetate and lowest in acetonitrile, while at 15 °C the growth rate is highest in acetonitrile. The growth rate data are further examined within the Burton Cabrera Franck (BCF) and the Birth and Spread (B+S) theories, and the results point to the importance of the surface diffusion step. Interfacial energies determined by fitting the B+S model to the growth rate data are well correlated to interfacial energies previously determined from primary nucleation data. Åke C. Rasmuson Department of Chemical and Environmental Science, University of Limerick, Limerick (Ireland) Email: [email protected] Tel: +353 61 234617

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Title Page Crystal Growth of Salicylic Acid in Organic Solvents Lijun Jia 1, Michael Svärd 1,2, Åke C. Rasmuson * 1,2 1


Abstract The crystal growth rate of salicylic acid has been determined by seeded isothermal desupersaturation experiments in different organic solvents (methanol, acetone, ethyl acetate and acetonitrile) and at different temperatures (10 °C, 15 °C, 20 °C and 25 °C). In situ ATRFTIR spectroscopy and principal component analysis (PCA) was employed for the determination of solution concentration. Activity coefficient ratios are approximately accounted for in the driving force determination. The results show that the dependence of the growth rate on the solvent at equal driving force varies with temperature, e.g. at 25 °C, the growth rate is highest in ethyl acetate and lowest in acetonitrile, while at 15 °C the growth rate is highest in acetonitrile. The growth rate data are further examined within the Burton Cabrera Franck (BCF) and the Birth and Spread (B+S) theories, and the results point to the importance of the surface diffusion step. Interfacial energies determined by fitting the B+S model to the growth rate data are well correlated to interfacial energies previously determined from primary nucleation data. Keywords: crystal growth, nucleation, active pharmaceutical ingredient, solvent, supersaturation, PCA, driving force, growth kinetics, interfacial energy


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Introduction Crystallization from solution is commonly used for separation and purification in the manufacturing of a wide variety of materials in the fine chemical, food and pharmaceutical industries.1-4 The organic solvent chosen for crystallization of an active pharmaceutical compound may strongly influence the nucleation and crystal growth rates, and thus the crystal quality, i.e. stability, bioavailability, morphology and crystal size distribution of the final crystal product. The activity coefficient of the solute in the solution depends on the solvent, and thus explains why the solubility depends on the solvent. However, this also leads to the true crystallization driving force being dependent on the solvent since these solutions are rarely ideal within a Raoult’s law framework.5-8 In addition, physical properties such as viscosity, polarity, surface energy and crystal-liquid interfacial energy all influence the crystallization behavior. The differences in solvent properties make it feasible to use the solvent as a probe to understand the mechanism of both nucleation7, 9, 10 and crystal growth11-14 at a molecular level. Efforts have been made to investigate the fundamental mechanisms of crystal growth and its associated kinetics mainly in two directions: determination of face growth rates15, 16 and the determination of particle overall growth rates.11, 17-21 In the first case, the crystal is often fixed for microscopic imaging and the transport resistance in the liquid phase can be significant unless the liquid flow is induced. For example, in the study of

face growth rates of

spontaneously nucleated crystals by Nguyen,22 there is no forced convection in the liquid, and the growth rates may not be representative of the intrinsic growth behavior. In the latter type, well-defined seeds are added to a supersaturated solution and suspended by agitation. The supersaturation often has to be low to avoid further nucleation, breakage or agglomeration, and the concentration decay has to be recorded with high accuracy. Cornell and Mazzotti17 reported the determination of crystal growth rates by recording solution concentrations using in situ ATR-FTIR and Raman spectroscopy without calibration. In our previous work,5 nucleation kinetics of salicylic acid was investigated using induction time and metastable zone width measurements, and the influence of the solvent was established. The difficulty of nucleation increases in the order: chloroform, ethyl acetate, acetonitrile, acetone, methanol and acetic acid. On the basis of the classical nucleation theory, the corresponding interfacial energies were determined. In following work,6 the nucleation behavior was correlated to the solvent-solute binding energy determined by spectroscopy, calorimetry, and density functional theory calculations. In the present paper, we report careful


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isothermal desupersaturation experiments to determine the crystal growth rate of salicylic acid in different solvents and at different temperatures. Empirical growth rate expressions and fundamental face growth models are fitted to the results. For comparison of the growth rate in the different solvents, particular attention is paid to the representation of the driving force, and the influence of the solvent on crystal growth is compared with that on the corresponding primary nucleation. Theory Crystal growth in supersaturated solution proceeds by bulk diffusion of growth units through the film, followed by step-wise desolvation, surface diffusion over the face and integration into the crystal lattice preferably at steps and kinks. The crystal growth rate is strongly dependent on the supersaturation, and in order to investigate and analyze the molecular level influence of the solvent on the growth process it is important to accurately account for the driving force. The chemical potential driving force can be expressed as a function of the ratio of solute activities according to equation (1). The activity of the solute, a, is in turn a product of the mole fraction concentration, x, and the solution activity coefficient, γ, defined within a Raoult’s law framework. Since it is experimentally non-trivial to determine activity coefficients, in particular at supersaturation, the influence of activity coefficients on the driving force is frequently neglected, and the driving force is represented by the supersaturation ratio S. In this work, S is taken as the ratio of concentrations expressed as solute to solvent weight ratios, c, kg solute/kg solvent.

∆ µ = RT ln

a xγ c = RT ln ≅ RT ln * a sat x sat γ sat c { S

(1)

When the surface integration step is rate-limiting, the crystal growth rate strongly depends on the crystal growth mechanism, which in turn is determined by the crystal surface properties. At moderate supersaturations, the crystal growth rate is governed by the presence of surface dislocations. In the BCF model,23 screw dislocations provide for constant supply of growth steps and the rate of growth is mainly determined by the rate of the propagation of these steps, which in turn depends on the step height, surface diffusion and surface defects24, 25:

G BCF =

AT (S − 1)(ln S ) tanh  B  B  T ln S 


(2)

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Γ * D surf V m A= x s2

B =

(3)

19 V m γ sl 2 kx s

(4)

where A is a parameter reflecting the crystal surface status and is here treated as temperaturedependent, Г* is the solute molecular adsorption coverage, and Dsurf is the surface diffusion coefficient, which here is expressed by an Arrhenius type equation (5):

 − Ea surf Dsurf = Asurf exp  RT

   

(5)

Parameter B incorporates physical properties of the crystal growth system, such as the solidliquid interfacial energy, γsl, and the molecular volume of the solute, Vm, and is considered independent of temperature in this work. Parameter k denotes the Boltzmann constant, and xs the diffusion mean free path over the surface. At higher supersaturation, the driving force is sufficient for surface nucleation to occur, by which new growth steps are introduced on the surface. The birth and spread mechanism (B+S model), describes the outgrowth of new crystalline layers initiated by such two-dimensional nucleation on the crystal surface, and is typically described by: 2 / 3 1/ 3 G B+ S = hν step Bstep = C (S − 1)

2/3

 16  C =  π 

1/ 3

h

1/ 6

γ  D = Vm h sl  3  k 

π

 Γ*  Dsurf  β '   xs 

−D   2  T ln S 

(ln S )1 / 6 exp 

(6)

2/3

(Vm ΓN A )5 / 6

(7)

2

(8)

where Bstep denotes the rate of two-dimensional nucleation, and νstep is the rate of step advancement. Parameters C and D are determined by the properties of the crystal growth system similar to the parameters A and B respectively of the BCF model. In the present work, C is treated as temperature-dependent, while D is considered temperature-independent, again using equation (5). The solid-liquid interfacial energy in equation (8) appears in formulae


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describing the radius of the two-dimensional critical nuclei that forms on the surface and is the source of new growth steps. In modeling of crystal size distributions, the growth rate is commonly expressed as the rate of increase of a characteristic linear dimension, L, of the crystals:

G=

dL dt

(10)

and often empirical power models are used to express the relation between the rate of increase of this linear dimension of the crystal and the supersaturation, either expressed as an absolute concentration difference, ∆c, or as a relative concentration ratio S-1. The rate constant is occasionally given temperature-dependence in accordance with an Arrhenius-type equation:

∆c  − Ea  g * G (s ) = k g0 exp   (s ) , s : ∆ c = c − c or S − 1 = * c  RT 

(11)

Experimental Materials and apparatus Salicylic acid (ACS reagent, ≥99.0%) purchased from Sigma-Aldrich was used without further purification. The solvents: Acetone (AC) (Sigma-Aldrich, ≥99.8%), Methanol (MeOH) (Sigma-Aldrich, ≥99.9%), Ethyl acetate (EA) (Sigma-Aldrich, ≥99.7%) and Acetonitrile (MeCN) (Sigma-Aldrich, ≥99.9%) were used as received. All the experiments in this work were performed in a jacketed, unbaffled 500 mL glass reactor with an inner diameter of 75 mm, equipped with a 4-pitched-blade PTFE coated impeller of diameter 60mm and placed approximately 15 mm above the bottom of the reactor. The temperature in the reactor was controlled by a heating and refrigeration circulator (Lauda, RE305 series) with a specified stability of ± 0.01oC. An attenuated total reflectance-Fourier transform infrared (ATR-FTIR) probe (Mettler-Toledo ReactIRTM iC 10) was utilized to measure the solution concentration in situ. The system operated in the mid-IR region, from 1900 cm-1 to 650 cm-2, and collected a spectrum every minute. A Mettler-Toledo focused beam reflectance (FBRM) probe was utilized in this work for in situ detection of nucleation (see the TOC figure). Procedures


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A salicylic acid solution of approximately 200 mL was prepared, introduced into the reactor and heated to 10 °C above the saturation temperature. An initial supersaturation ratio (S0 = c0/c*) was obtained by quickly cooling down the solution to the experimental temperature (10 °C, 15 °C, 20 °C or 25 °C). This cooling required approx. 10 min depending on the solution and the final temperature. When the temperature was stabilized (when the intensity of a characteristic FTIR peak of salicylic acid is stable), a known amount of seed crystals from sieve fraction 125 µm – 250 µm was introduced into the solution under agitation at 180 rpm. In order to avoid nucleation, the initial supersaturation is low (S AC > MeCN > EA. Comparing equations (4) and (8), an important parameter for the dependence of these parameters on the solvent is the interfacial energy. In the BCF-model the interfacial energy occurs in the equation as a transformation of the edge energy of the growth step. The edge energy determines the radius of the critical two-dimensional nucleus that determines the radius of the Archimedes spiral describing the screw dislocation. The higher the edge energy the greater the distance between two adjacent steps, and the longer becomes the average distance of surface diffusion. In the B+S model, the solid-liquid interfacial energy in equation (8) appears in formula describing the radius of the two-dimensional critical nuclei that forms on the surface and is the source of new growth steps. Using the D value obtained by fitting the B+S model, interfacial energies have been estimated from crystal growth data by assuming the height of the growth step: h (0.54 nm) to be equal to the cubic root of the molecular volume of


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salicylic acid, Vm (0.159 nm3) as obtained from the crystal density. (Of course, the growth step height will be different on different faces and this value is taken as a first estimate of the average). Results are given in Table 5, and we may note that the interfacial energy depends on

2

the solvent and decays in the order: MeOH > AC > MeCN > EA.

Interfacial energy, mJ/m

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


4.13 5

3.81

nucleation crystal growth

2.4

1.10

1.82 0.79 0.58

EA

0.65

MeCN

AC

MeOH

Figure 10. Comparison of interfacial energies obtained from the B+S crystal growth model with values obtained using the classical nucleation theory from Mealey et al. (2015).5 It is widely accepted that the solid-liquid interfacial energy, γsl, appears as a governing parameter also in crystal nucleation. A detailed account of the classical nucleation theory can be found in previous publications36 and in many monographs. The rate of homogeneous primary three-dimensional nucleation can be expressed as:

J = kCs Cns D∆µ

 16π γ sl3Vm2   B  1  = An exp − n 2  exp − 2  kTγ sl  T∆µ   3kT ∆µ 

(9)

where the interfacial energy determines the thermodynamic barrier for the formation of nuclei (the exponential term), but also appear in the Zeldovich factor36 and thus also influences the pre-exponential factor, An. From nucleation experiments the interfacial energy can be extracted within the classical nucleation theory framework, as previously reported.5 In Figure 10, interfacial energies obtained by the B+S model from crystal growth data in the present work, which are compared with values previously reported from nucleation experiments. The order of the solvents with respect to increasing interfacial energy is the same. It is notable that the value of the interfacial energy calculated from the growth rate data are approximately ¼ of those obtained from nucleation data. We should expect the interfacial energy for 3-D nucleation to be higher than that of 2-D nucleation since in the later case part of the nucleous has a more


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favorable contact with the crystalline face on which it is nucleating. Mazzotti37 reported that the interfacial energy obtained from heterogeneous nucleation is less than half of the values obtained from homogeneous nucleation in the same experimental conditions.

Conclusions This work shows that accurate representation of the driving force is of great importance for determination of correct supersaturation and temperature dependence of crystal growth rates. The crystal growth rate of salicylic acid at equal driving force depends on the solvent, but the order among the solvents changes with temperature, reflecting a significant difference in the apparent activation energy. The results of fitting growth rate data to the Burton Cabrera Franck (BCF) and the Birth and Spread (B+S) models, suggest that surface diffusion is an important step in the growth process. The determined surface diffusion activation energy decreases in the order: ethyl acetate ≥ methanol> acetone > acetonitrile. The solid-liquid interfacial energy extracted from the growth experiments within the B+S model increases in the order: ethyl acetate < acetonitrile < acetone < methanol, the order being the same as that previously reported for interfacial energies obtained from nucleation experiments. However, as expected, the values from the growth rate data are lower reflecting that 3-D nucleation is more difficult than 2-D nucleation. Acknowledgment Financial support of the Science Foundation Ireland (12/RC/2275) is gratefully acknowledged. Notation a

Activity

A

BCF model parameter, K m/s

Asurf

pre-exponential factor of surface diffusion equation, m2/sB BCF model parameter, K

Bstep

two-dimensional nucleation rate

c

solution concentration, kg/m3 or kg solute/kg solvent

c*

solubility, kg/m3 or kg solute/kg solvent

Cs

concentration of solute molecules


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Cns

concentration of all molecules in solution

C

B+S model parameter, m/s

∆c

absolute supersaturation, kg solute/kg solvent

D

B+S model parameter, K2

Dsurf

surface diffusion coefficient, m2/s

Ea

apparent activation energy, kJ/mol

Ea,surf activation energy of surface diffusion of adsorbed molecules, kJ/mol G

crystal growth rate, m/s

g

power of driving force in power law growth models, dimensionless

k

Boltzmann constant, m2 kg/s2/k

kd

mass transfer coefficient, m/s/(kg/m3)

kg

parameter in power law growth models (pre-exponential factor), unit changes with the term of the driving force

R

gas constant, J/K/mol

S

supersaturation ratio, dimensionless

S-1

relative supersaturation, dimensionless

s

supersaturation term in power law equation, Eq 11, either representing (∆c) or (S-1)

Vm

molecular volume, m3

x

mole fraction concentration, dimensionless

xs

mean diffusion distance on the surface, m

Greek letters γsl

interfacial energy between solid and liquid, J/m2

γ

activity coefficient

ρc

crystal density, kg/m3

µ

chemical potential, J/mol


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∆µ

chemical potential difference, J/mol

νstep

step advancement rate in the B+S model

Г

concentration of surface - adsorbed molecules, mol/m2

Г*

equilibrium concentration of surface - adsorbed molecules, molecules/m2

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Supporting information The supporting information includes the solution properties consisting of solubility and activity coefficients, and modified power law fitting plot showing the kinetics of crystal growth. References (1) Chen, J.; Sarma, B.; Evans, J. M. B.; Myerson, A. S., Pharmaceutical Crystallization. Crystal Growth & Design 2011, 11, 887-895. (2) Vekilov, P. G., Nucleation. Crystal Growth & Design 2010, 10, 5007-5019. (3) Paul, E. L.; Tung, H.-H.; Midler, M., Organic crystallization processes. Powder Technology 2005, 150, 133-143. (4) Tung, H.-H., Industrial Perspectives of Pharmaceutical Crystallization. Organic Process Research & Development 2013, 17, 445-454. (5) Mealey, D.; Croker, D. M.; Rasmuson, A., Crystal nucleation of salicylic acid in organic solvents. CrystEngComm 2015. (6) Khamar, D.; Zeglinski, J.; Mealey, D.; Rasmuson, Å. C., Investigating the Role of Solvent–Solute Interaction in Crystal Nucleation of Salicylic Acid from Organic Solvents. Journal of the American Chemical Society 2014, 136, 11664-11673. (7) Yang, H.; Rasmuson, Å. C., Nucleation of Butyl Paraben in Different Solvents. Crystal Growth & Design 2013, 13, 4226-4238. (8) Matsuda, H.; Kaburagi, K.; Matsumoto, S.; Kurihara, K.; Tochigi, K.; Tomono, K., Solubilities of Salicylic Acid in Pure Solvents and Binary Mixtures Containing Cosolvent†. Journal of Chemical & Engineering Data 2008, 54, 480-484. (9) Mealey, D.; Zeglinski, J.; Khamar, D.; Rasmuson, A. C., Influence of solvent on crystal nucleation of risperidone. Faraday Discussions 2015, 179, 309-328. (10) Yang, H.; Svärd, M.; Zeglinski, J.; Rasmuson, Å. C., Influence of Solvent and SolidState Structure on Nucleation of Parabens. Crystal Growth & Design 2014, 14, 3890-3902. (11) Zhang, X.; Zhang, S.; Sun, X.; Yin, Z.; Liu, Q.; Zhang, X.; Yin, Q., Nucleation and growth mechanism of cefodizime sodium at different solvent compositions. Front. Chem. Sci. Eng. 2013, 7, 490-495. (12) Rashid, A.; White, E. T.; Howes, T.; Litster, J. D.; Marziano, I., Growth rates of ibuprofen crystals grown from ethanol and aqueous ethanol. Chemical Engineering Research and Design 2012, 90, 158-161. (13) Ó’Ciardhá, C. T.; Mitchell, N. A.; Hutton, K. W.; Frawley, P. J., Determination of the Crystal Growth Rate of Paracetamol As a Function of Solvent Composition. Industrial & Engineering Chemistry Research 2012, 51, 4731-4740. (14) Mitchell, N. A.; Ó'Ciardhá, C. T.; Frawley, P. J., Estimation of the growth kinetics for the cooling crystallisation of paracetamol and ethanol solutions. Journal of Crystal Growth 2011, 328, 39-49.


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(15) Kimia, J.; Brojonegoro, J. S., In Situ Measurement of the Growth Rate of the (111) Face of Borax Single Crystal. Jurnal Matematika dan Sains 2005, 10, 101-106. (16) Wang, X. Z.; Calderon De Anda, J.; Roberts, K. J., Real-Time Measurement of the Growth Rates of Individual Crystal Facets Using Imaging and Image Analysis: A Feasibility Study on Needle-shaped Crystals of L-Glutamic Acid. Chemical Engineering Research and Design 2007, 85, 921-927. (17) Cornel, J.; Mazzotti, M., Estimating Crystal Growth Rates Using in situ ATR-FTIR and Raman Spectroscopy in a Calibration-Free Manner. Industrial & Engineering Chemistry Research 2009, 48, 10740-10745. (18) Scholl, J.; Lindenberg, C.; Vicum, L.; Brozio, J.; Mazzotti, M., Precipitation of [small alpha] l-glutamic acid: determination of growth kinetics. Faraday Discussions 2007, 136, 247264. (19) Qiu, Y.; Rasmuson, Å. C., Estimation of crystallization kinetics from batch cooling experiments. AIChE Journal 1994, 40, 799-812. (20) Qiu, Y.; Rasmuson, Å. C., Nucleation and growth of succinic acid in a batch cooling crystallizer. AIChE Journal 1991, 37, 1293-1304. (21) Qiu, Y.; Rasmuson, Å. C., Growth and dissolution of succinic acid crystals in a batch stirred crystallizer. AIChE Journal 1990, 36, 665-676. (22) Nguyen, T. T. H.; Hammond, R. B.; Roberts, K. J.; Marziano, I.; Nichols, G., Precision measurement of the growth rate and mechanism of ibuprofen {001} and {011} as a function of crystallization environment. CrystEngComm 2014, 16, 4568-4586. (23) Burton, W. K.; Cabrera, N.; Frank, F. C., The Growth of Crystals and the Equilibrium Structure of their Surfaces. Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences 1951, 243, 299-358. (24) Markov, I. V., Crystal Growth for Beginners: Fundamentals of Nucleation, Crystal Growth and Epitaxy. ed.; World Scientific: 2003. (25) Mersmann, A., Crystallization Technology Handbook. Drying Technology 1995, 13, 1037-1038. (26) Svärd, M.; Rasmuson, Å. C., (Solid + liquid) solubility of organic compounds in organic solvents – Correlation and extrapolation. The Journal of Chemical Thermodynamics 2014, 76, 124-133. (27) Valavi, M.; Svärd, M.; Rasmuson, Å. C., Improving Estimates of the Crystallization Driving Force: Investigation into the Dependence on Temperature and Composition of Activity Coefficients in Solution. Crystal Growth & Design 2016, 16, 6951-6960. (28) Nordström, F. L.; Rasmuson, Å. C., Solubility and Melting Properties of Salicylic Acid. J. Chem. Eng. Data 2006, 51, 1668-1671. (29) Olafson, K. N.; Ketchum, M. A.; Rimer, J. D.; Vekilov, P. G., Molecular Mechanisms of Hematin Crystallization from Organic Solvent. Crystal Growth & Design 2015, 15, 55355542. (30) Chen, K.; Vekilov, P. G., Evidence for the surface-diffusion mechanism of solution crystallization from molecular-level observations with ferritin. Physical Review E 2002, 66, 021606. (31) Vekilov, P. G., Phase transitions of folded proteins. Soft Matter 2010, 6, 5254-5272. (32) Bennema, P., The importance of surface diffusion for crystal growth from solution. Journal of Crystal Growth 1969, 5, 29-43. (33) Mullin, J. W., Crystallization. ed.; 2001. (34) Radenović, N.; van Enckevort, W.; Verwer, P.; Vlieg, E., Growth and characteristics of the {1 1 1} NaCl crystal surface grown from solution. Surface Science 2003, 523, 307-315. (35) Reichardt, C.; Welton, T., Solvents and solvent effects in organic chemistry. ed.; John Wiley & Sons: 2011.


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(36) Nordstrom, F. L.; Svard, M.; Rasmuson, A. C., Primary nucleation of salicylamide: the influence of process conditions and solvent on the metastable zone width. CrystEngComm 2013, 15, 7285-7297. (37) Lindenberg, C.; Mazzotti, M., Effect of temperature on the nucleation kinetics of α lglutamic acid. J. Cryst. Growth 2009, 311, 1178-1184.


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For Table of Contents Use Only Crystal Growth of Salicylic Acid in Organic Solvents Lijun Jia 1, Michael Svärd 1,2, Åke C. Rasmuson * 1,2 1


Synopsis The crystal growth of salicylic acid in organic solvents has been studied in seeded isothermal desupersaturation experiments. Principal component analysis (PCA) was applied to IR spectra analysis for the determination of solution concentration. The crystal growth rates were compared in organic solvents at the same driving force considering activity coefficient and growth mechanisms were discussed.


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Footnote In ethyl acetate at 20 oC, in spite of several attempts, we were not able to avoid crystal nucleation during the experiments and hence no valid crystal growth rates could be determined.


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Crystal Growth of Salicylic Acid in Organic Solvents - ACS Publications

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