Abstract
The knowledge of stable and metastable heterogeneous equilibria is paramount for the rational management of separation/purification processes based on crystallization.
Starting from a collection of binary and ternary phase diagrams the design of crystallization processes is illustrated by careful details on different pathways corresponding to crystallizations induced by: (i) cooling (ii) antisolvent (iii) evaporation. By taking into account the stable and metastable heterogeneous equilibria, the access to different final or transient states are detailed. The fine analyses of the pathways inside the relevant phase diagrams also lead to assess the robustness of the processes including their risks of lack of control. In addition, the thermodynamic optimum yield can be reckoned and thus, the tuning of the kinetic parameters can be framed within sensible limits.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Abbreviations
- <P>:
-
symbolizes crystals of compound or component P
- Mixed solvate::
-
at least two different solvent molecules are incorporated in the same crystallographic site.
- Heterosolvate::
-
at least two different solvent molecules are incorporated in two different crystallographic sites.
- Efflorescence::
-
release of solvent molecules in the gas phase by either: a solvate, a mixed solvate or a heterosolvate.
- Deliquescence::
-
uptake of solvent from the gas phase up to dissolution of the crystals (often applied to moisture uptake and aqueous solution). This phenomenon can be followed by the recrystallization of a solvate (hydrate in case of moisture uptake).
- u.s.s.::
-
Undersaturated solution i.e. monophasic domain with a single liquid phase.
- Non-congruent soluble compound::
-
In a ternary system, the line connecting the point representative of the solid and that of the solvent does not intersect the stable solubility curve of the compound. In order to crystallize that compound in solution without any trace of any other solid, an excess of one component has to be added in the system. A compound can have a non-congruent solubility at one temperature and a congruent solubility at another temperature.
- Binary eutectic::
-
Three phase invariant which involves the simultaneous and reversible crystallization and melting of two solids from (to give) a liquid. The temperature and the composition of the three phases are fixed.
- Ternary eutectic::
-
four phase invariant which involves the simultaneous and reversible crystallization and melting of three solids from (to give) a liquid. The temperature and the composition of the four phases are fixed.
- Binary peritectic (non-congruent fusion)::
-
Three phase invariant involving two solid phases and one liquid, all of them of specific compositions. At a defined temperature, it corresponds to the reversible decomposition of an intermediate compound on heating.
- Binary monotectic (stable miscibility gap at high temperature)::
-
Three phase invariant involving two liquids and one solid, all of them of specific compositions. At a defined temperature, it corresponds to the reversible decomposition of a liquid into a solid phase and another liquid on cooling.
- RH::
-
relative humidity. This is a ratio (thus non unit) valid at a fixed temperature and defined as: the vapor pressure of water in the system over the saturated vapor pressure.
References
Ricci JE (1966) The phase rule and heterogeneous equilibrium. Dover Publications Inc., New York
Findlay A (1904) The phase rule and its applications. Longmans, Green and Co, London
Zernike J (1955) Chemical phase theory. A comprehensive treatise on the deduction, the application and the limitations of the phase rule.; N.V. Uitgevers-Maatschappij E. Kluwer: Dventer-Antwerp-Djakarta
Hillert M (1998) Phase equilibria, phase diagrams, phase transformations. Their thermodynamic basis. Cambridge University Press, Cambridge
Coquerel G (2015) J Pharm Pharmacol 67:869–878
Coquerel G (2014) Chem Soc Rev 43:2286–2300
Coquerel G (2006) Chem Eng Technol 29(2):182–186
Coquerel G (2000) Enantiomer 5:481
Viedma C, Coquerel G., Cintas P (2015) Crystallization of chiral molecules. In: T. Nishinaga (ed) Handbook of crystal growth, volume IA: fundamentals: thermodynamics and kinetics, Elsevier, Amsterdam ISBN: 9780444563699:951–1002
Coquerel G (2006) Chem Eng Process 45:857–862
Coquerel G (2007) Preferential crystallization in topics in current chemistry novel optical resolution technologies. (ed) Springer GmbH, ISSN: 0340-1022: 1–50
Courvoisier L, Mignot L, Petit MN, Coquerel G (2003) Org Process Res Dev 7:1007–1016
Ostwald WZ (1897) Phys Chem 119:227
Veesler S, Lafferrère L, Garcia E, Hoff C (2003) Org Process Res Dev 7:983
Bonnett PE, Carpenter KJ, Dawson S, Davey RJJ (2003) Chem Commun 21(6):698–699
Codan L, Bäbler MU, Mazzotti M (2010) Cryst Growth Des 10:4005
Brandel C, Gbabode G, Cartigny Y, Martin C, Gouhier G, Petit S, Coquerel G (2014) Chem Mater 26(14):4151
Mullin J W (2001) Crystallization, 4th edn. Butterworth Heinemann, ISBN 0 7506 4833 3
Mahieux J, Sanselme M, Harthong S, Melan C, Aronica C, Guy L, Coquerel G (2013) Cryst Growth Des 13(8):3621–3631
Fours B, Cartigny Y, Petit, S Coquerel, G (2015) Faraday Discuss 179:475-488
Authelin J-R (2005) Int J Pharm 303:37–53
Couvrat N, Cartigny Y, Linol J, Vaysse-Ludot L, Langlois P, Coquerel G (2015) Chem Eng Technol 38(6):999–1005
Coquerel G (2012) ‘Co-crystals and beyond’ ch 13 in ‘Pharmaceutical salts and co-crystal’ RSC Publishing, Editors: Johan Wouters and Luc Quéré ISBN: 978-1-84973-158-4:300–317
Prigogine I (1961) Introduction to thermodynamics of irreversible processes. Interscience, New York
Acknowledgements
Dr M-N Delauney is thanked for her important contribution in the illustrations.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2017 Springer Science+Business Media B.V.
About this chapter
Cite this chapter
Coquerel, G. (2017). Phase Diagrams for Process Design. In: Roberts, K., Docherty, R., Tamura, R. (eds) Engineering Crystallography: From Molecule to Crystal to Functional Form. NATO Science for Peace and Security Series A: Chemistry and Biology. Springer, Dordrecht. https://doi.org/10.1007/978-94-024-1117-1_12
Download citation
DOI: https://doi.org/10.1007/978-94-024-1117-1_12
Published:
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-024-1115-7
Online ISBN: 978-94-024-1117-1
eBook Packages: Biomedical and Life SciencesBiomedical and Life Sciences (R0)