Dilution wave and negative-order crystallization kinetics of chain molecules.
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.
Ungar
G
G
Department of Engineering Materials, University of Sheffield, Sheffield S1 3JD, United Kingdom. g.ungar@sheffield.ac.uk
Mandal
P K
PK
Higgs
P G
PG
de Silva
D S
DS
Boda
E
E
Chen
C M
CM
D003460:Crystallization; D007700:Kinetics; D046911:Macromolecular Substances; D011108:Polymers / Q000737:chemistry*; D011487:Protein Conformation
D046911:Macromolecular Substances; D011108:Polymers