From Rate Measurements to Mechanistic Data for Condensed Matter Reactions: A Case Study Using the Crystallization of [Zn(OH2)6][ZnCl4]

Hillis, Berkley; Losey, Bradley; Weng, James; Ghaleb, Nezar; Hou, Feier; Martin, James

doi:10.3390/cryst7010011

From Rate Measurements to Mechanistic Data for Condensed Matter Reactions: A Case Study Using the Crystallization of [Zn(OH₂)₆][ZnCl₄]

Journal Article · Fri Dec 30 23:00:00 EST 2016 · Crystals

DOI:https://doi.org/10.3390/cryst7010011· OSTI ID:1368279

Hillis, Berkley ^[1]; Losey, Bradley ^[1]; Weng, James ^[1]; Ghaleb, Nezar ^[1]; Hou, Feier ^[1]; Martin, James ^[1]

North Carolina State Univ., Raleigh, NC (United States)

The kinetics of crystallization of the R = 3 hydrate of zinc chloride, [Zn(OH₂)₆][ZnCl₄], is measured by time-resolved synchrotron x-ray diffraction, time-resolved neutron diffraction, and by differential scanning calorimetry. It is shown that analysis of the rate data using the classic Kolmogorov, Johnson, Mehl, Avrami (KJMA) kinetic model affords radically different rate constants for equivalent reaction conditions. Reintroducing the amount of sample measured by each method into the kinetic model, using our recently developed modified-KJMA model (M-KJMA), it is shown that each of these diverse rate measurement techniques can give the intrinsic, material specific rate constant, the velocity of the phase boundary, v_pb. These data are then compared to the velocity of the crystallization front directly measured optically. The time-resolved diffraction methods uniquely monitor the loss of the liquid reactant and formation of the crystalline product demonstrating that the crystallization of this hydrate phase proceeds through no intermediate phases. The temperature dependent v_pb data are then well fit to transition zone theory to extract activation parameters. These demonstrate that the rate-limiting component to this crystallization reaction is the ordering of the waters (or protons) of hydration into restricted positions of the crystalline lattice resulting in large negative entropy of activation.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1368279

Journal Information:: Crystals, Journal Name: Crystals Journal Issue: 1 Vol. 7; ISSN 2073-4352

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited By (1)

Precise implications for real-space pair distribution function modeling of effects intrinsic to modern time-of-flight neutron diffractometers Olds, Daniel; Saunders, Claire N.; Peters, Megan Acta Crystallographica Section A Foundations and Advances, Vol. 74, Issue 4 https://doi.org/10.1107/s2053273318003224	journal	June 2018

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Related Subjects

36 MATERIALS SCIENCE
crystalline hydrate
crystallization
kinetics
mechanism
phase transition
time-resolved diffraction