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

Journal Article · · Crystals
DOI:https://doi.org/10.3390/cryst7010011· OSTI ID:1368279
 [1];  [1];  [1];  [1];  [1];  [1]
  1. North Carolina State Univ., Raleigh, NC (United States)
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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, vpb. 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 vpb 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.

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, Vol. 7, Issue 1; ISSN 2073-4352
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

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