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Diffusion-limited kinetics of the solution-solid phase transition of molecular substances.

ABSTRACT: For critical tests of whether diffusion-limited kinetics is an option for the solution-solid phase transition of molecular substances or whether they are determined exclusively by a transition state, we performed crystallization experiments with ferritin and apoferritin, a unique pair of proteins with identical shells but different molecular masses. We find that the kinetic coefficient for crystallization is identical (accuracy

SUBMITTER: Petsev DN

PROVIDER: S-EPMC298680 | biostudies-literature | 2003 Feb

REPOSITORIES: biostudies-literature

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Diffusion-limited kinetics of the solution-solid phase transition of molecular substances.

Petsev Dimiter N DN Chen Kai K Gliko Olga O Vekilov Peter G PG

Proceedings of the National Academy of Sciences of the United States of America 20030124 3

For critical tests of whether diffusion-limited kinetics is an option for the solution-solid phase transition of molecular substances or whether they are determined exclusively by a transition state, we performed crystallization experiments with ferritin and apoferritin, a unique pair of proteins with identical shells but different molecular masses. We find that the kinetic coefficient for crystallization is identical (accuracy <or=7%) for the pair, indicating diffusion-limited kinetics of cryst ...[more]

PMID: 12552115

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Project description:The coupled multicomponent diffusion of the species Ca2Si2O6, CaAl2SiO6 and Mg2Si2O6 was determined in diopside crystals in the diopside/anorthite (Di/An) system at temperatures (T) of 1110-1260 °C and oxygen fugacities (fO 2 ) between 1.0 log unit below and above the fayalite-magnetite-quartz equilibrium (FMQ ± 1). Diffusion couples were prepared by the seed overgrowth technique. Element concentration profiles were measured perpendicular to the rim/core interface by step-scanning profiling with a field emission gun scanning electron microscope (FEG-SEM). The multicomponent diffusion matrix was solved by fitting its eigenvalues (λ) and eigenvectors (v) to the measured concentration profiles. The full diffusion matrix D can be recovered by using the formula D = P Λ P - 1 resulting in the following equation: D Di/An = 1.00 - 0.67 - 0.38 1.00 λ 1 T 0 0 λ 2 T 1.00 - 0.67 - 0.38 1.00 - 1 . The eigenvalues (λ1 and λ2) represent upper limit values and are described by the following Arrhenius-type equations: λ 1 Di/An = 10 - 15.98 ± 1.17 × exp - 114.4 ± 32.8 kJ/mol RT , λ 2 Di/An = 10 - 16.23 ± 1.17 × exp - 114.4 ± 32.8 kJ/mol RT , where λ1 and λ2 are the first and second eigenvalue of the diffusion matrix in m2 s-1 , R is the gas constant and T is the temperature in K. The dominant eigenvalue (λ1) is one quarter order of magnitude larger than the second eigenvalue (λ2). The eigenvectors are constant for all experiments inferring that the entire D matrix can be described with the eigenvalues as the only T-dependent parameter. Additionally, the derived diffusion data and modeling approach were applied to constrain the duration of magmatic processes recorded in zoned clinopyroxene (cpx) phenocrysts from a basaltic, post-plutonic dyke of the Tertiary Adamello batholiths (N-Italy). The results reveal residence times of the overgrown cpx prior to final emplacement in the range of 0.25-1.7 years (lower limit values) testifying that the data and method can be applied to model cpx diffusion profiles in complex natural cpx.

Dataset Information

Diffusion-limited kinetics of the solution-solid phase transition of molecular substances.

Publications

Diffusion-limited kinetics of the solution-solid phase transition of molecular substances.

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