title: Dilution wave and negative-order crystallization kinetics of chain molecules.
abstract: We show that the crystal growth rate of a very long-chain n-alkane C C(198)H(398) from solution can decrease with increasing supersaturation and follow strongly negative order kinetics. The experimental behavior can be well represented by a theoretical model which allows the molecule to attach and detach as either extended or folded in two. The obstruction of extended-chain growth by unstable folded depositions increases disproportionately with increasing concentration. As a consequence of this abnormal kinetics, a "dilution wave" can propagate and trigger a folded-to-extended-chain transformation on its way.
authors.affiliation: Department of Engineering Materials, University of Sheffield, Sheffield S1 3JD, United Kingdom. g.ungar@sheffield.ac.uk
authors.forename: G
authors.initials: G
authors.lastname: Ungar
authors.forename: P K
authors.initials: PK
authors.lastname: Mandal
authors.forename: P G
authors.initials: PG
authors.lastname: Higgs
authors.forename: D S
authors.initials: DS
authors.lastname: de Silva
authors.forename: E
authors.initials: E
authors.lastname: Boda
authors.forename: C M
authors.initials: CM
authors.lastname: Chen
mesh_terms: D003460:Crystallization; D007700:Kinetics; D046911:Macromolecular Substances; D011108:Polymers / Q000737:chemistry*; D011487:Protein Conformation
chemical_list: D046911:Macromolecular Substances; D011108:Polymers