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Title: High pressure studies of potassium perchlorate

Abstract

Two experiments are reported on KClO 4 at extreme conditions. A static high pressure Raman study was first conducted to 18.9 GPa. Evidence for at least two new phases was observed: one between 2.4 and 7.7 GPa (possibly sluggish), and the second near 11.7 GPa. Then, the X-ray induced decomposition rate of potassium perchlorate (KClO 4 hv→ KCl + 2O 2) was studied up to 15.2 GPa. The time-dependent growth of KCl and O 2 was monitored. The decomposition rate slowed at higher pressures. As a result, we present the first direct evidence for O 2 crystallization at higher pressures, demonstrating that O 2 molecules aggregate at high pressure.

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [1]
  1. Univ. of Nevada, Las Vegas, NV (United States)
  2. Univ. of Nevada, Las Vegas, NV (United States); Carnegie Inst. of Washington, Argonne, IL (United States)
Publication Date:
Research Org.:
Univ. of Nevada, Las Vegas, NV (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1332633
Grant/Contract Number:
NA0001982; FC08-01NV14049; NA0001974; FG02-99ER45775
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Physics Letters
Additional Journal Information:
Journal Volume: 660; Journal Issue: C; Journal ID: ISSN 0009-2614
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
73 NUCLEAR PHYSICS AND RADIATION PHYSICS; useful hard x-ray photochemistry; high pressure; oxygen; kclo4 decomposition

Citation Formats

Pravica, Michael, Wang, Yonggang, Sneed, Daniel, Reiser, Sharissa, and White, Melanie. High pressure studies of potassium perchlorate. United States: N. p., 2016. Web. doi:10.1016/j.cplett.2016.07.060.
Pravica, Michael, Wang, Yonggang, Sneed, Daniel, Reiser, Sharissa, & White, Melanie. High pressure studies of potassium perchlorate. United States. doi:10.1016/j.cplett.2016.07.060.
Pravica, Michael, Wang, Yonggang, Sneed, Daniel, Reiser, Sharissa, and White, Melanie. 2016. "High pressure studies of potassium perchlorate". United States. doi:10.1016/j.cplett.2016.07.060. https://www.osti.gov/servlets/purl/1332633.
@article{osti_1332633,
title = {High pressure studies of potassium perchlorate},
author = {Pravica, Michael and Wang, Yonggang and Sneed, Daniel and Reiser, Sharissa and White, Melanie},
abstractNote = {Two experiments are reported on KClO4 at extreme conditions. A static high pressure Raman study was first conducted to 18.9 GPa. Evidence for at least two new phases was observed: one between 2.4 and 7.7 GPa (possibly sluggish), and the second near 11.7 GPa. Then, the X-ray induced decomposition rate of potassium perchlorate (KClO4 hv→ KCl + 2O2) was studied up to 15.2 GPa. The time-dependent growth of KCl and O2 was monitored. The decomposition rate slowed at higher pressures. As a result, we present the first direct evidence for O2 crystallization at higher pressures, demonstrating that O2 molecules aggregate at high pressure.},
doi = {10.1016/j.cplett.2016.07.060},
journal = {Chemical Physics Letters},
number = C,
volume = 660,
place = {United States},
year = 2016,
month = 7
}

Journal Article:
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  • Two static high-pressure X-ray diffraction (XRD) studies of potassium chlorate have been performed at pressures of up to {approx}14.3 GPa in a diamond anvil cell at ambient temperature using the 16 ID-B undulator beamline at the Advanced Photon Source for the X-ray source. The first experiment was conducted to ascertain decomposition rates of potassium chlorate as a function of pressure. Below 2 GPa, the sample was observed to decompose rapidly in the presence of the X-ray beam and release oxygen. Above 2 GPa (near the phase I phase II transition), the decomposition rate dramatically slowed so that good quality XRDmore » patterns could be acquired. This suggests a phase-dependent decomposition rate. In the second study, X-ray diffraction spectra were collected at pressures from 2 to 14.3 GPa by aligning virgin portions of the sample into the focused X-ray beam at each pressure. The results suggest the co-existence of mixed monoclinic (I) and rhombohedral (II) phases of potassium chlorate near 2 GPa. At pressures beyond 4 GPa, the XRD patterns show a very good fit to KClO{sub 3} in the rhombohedral phase with space group R3m, in agreement with earlier studies. No further phase transitions were observed with pressure. Decompression of the sample to ambient pressure indicated mixed phases I and II coupled with a small amount of synchrotron X-ray-induced decomposition product. The equation of state within this pressure regime has been determined.« less
  • Acetic acid exchange of manganese(II) perchlorate and manganese(II) acetate in acetic acid (HOAc) involving dichloromethane-d/sub 2/ as a diluent has been studied at various pressures up to 180 MPa by the variable-pressure /sup 17/O FT-NMR line-broadening method. The activation volumes at 258 K are +0.4 /plus minus/ 0.7 cm/sup 3/ mol/sup /minus/1/ for Mn(ClO/sub 4/)/sub 2/ and +6.7 /plus minus/ 0.6 cm/sup 3/ mol/sup /minus/1/ for Mn(OAc)/sub 2/, respectively. These positive values are unusual for the solvent exchange on manganese(II) studied so far and are discussed in terms of the bulkiness of acetic acid molecules and the effect of themore » ligand bound to the manganese(II). 26 references, 4 figures, 2 tables.« less