Zirconium tetrachloride revisited

Borjas Nevarez, Rosendo; Balasekaran, Samundeeswari Mariappan; Kim, Eunja; Weck, Philippe; Poineau, Frederic

doi:10.1107/S205322961800219X

Title: Zirconium tetrachloride revisited

Abstract

We present that zirconium tetrachloride, ZrCl₄, is a strategic material with wide-ranging applications. Until now, only one crystallographic study on ZrCl₄has been reported [Krebs (1970).Z. Anorg. Allg. Chem.378, 263–272] and that was more than 40 years ago. The compound used for the previous determination was prepared from ZrO₂ and Cl₂–CCl₄, and single-crystal X-ray diffraction (SCXRD) studies on ZrCl₄ obtained from Zr metal have not yet been reported. In this context, we prepared ZrCl₄ from the reaction of Zr metal and Cl₂ gas in a sealed tube and investigated its structure at 100, 150, 200, 250, and 300 K. At 300 K, the SCXRD analysis indicates that ZrCl₄ crystallizes in the orthorhombic space group Pca2₁ [a= 6.262 (9),b= 7.402 (11),c= 12.039 (17) Å, andV= 558.0 (14) Å³] and consists of infinite zigzag chains of edge-sharing ZrCl₆ octahedra. This chain motif is similar to that observed previously in ZrCl₄, but the structural parameters and space group differ. Finally, in the temperature range 100–300 K, no phase transformation was identified, while elongation of intra-chain Zr...Zr [3.950 (1) Å at 100 K and 3.968 (5) Å at 300 K] and inter-chain Cl...Cl [3.630 (3) Å at 100 K and 3.687 (9) Å at 300more » K] distances occurred.« less

Authors:

Borjas Nevarez, Rosendo ^[1]; Balasekaran, Samundeeswari Mariappan ^[1];

^[2]; Weck, Philippe ^[3]; Poineau, Frederic ^[1]

Univ. of Nevada, Las Vegas, NV (United States). Department of Chemistry and Biochemistry
Univ. of Nevada, Las Vegas, NV (United States). Department of Physics and Astronomy
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Publication Date:: Mon Feb 19 00:00:00 EST 2018

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5); USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1429669

Report Number(s):: SAND-2017-11627J
Journal ID: ISSN 2053-2296; ACSCGG; 658195

Grant/Contract Number:: AC04-94AL85000; NE0008449; NA0003525

Resource Type:: Accepted Manuscript

Journal Name:: Acta Crystallographica. Section C, Structural Chemistry (Online)

Additional Journal Information:: Journal Name: Acta Crystallographica. Section C, Structural Chemistry (Online); Journal Volume: 74; Journal Issue: 3; Journal ID: ISSN 2053-2296

Publisher:: International Union of Crystallography

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; zirconium tetrachloride; crystal structure; chain motif; temperature study

Citation Formats


                    Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, and Poineau, Frederic. Zirconium tetrachloride revisited.  United States: N. p., 2018. 
Web.  doi:10.1107/S205322961800219X.

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                    Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, & Poineau, Frederic. Zirconium tetrachloride revisited.  United States.  https://doi.org/10.1107/S205322961800219X

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                    Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, and Poineau, Frederic. Mon .  
"Zirconium tetrachloride revisited".  United States.  https://doi.org/10.1107/S205322961800219X.  https://www.osti.gov/servlets/purl/1429669.

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@article{osti_1429669,

  title        = {Zirconium tetrachloride revisited},

  author       = {Borjas Nevarez, Rosendo and Balasekaran, Samundeeswari Mariappan and Kim, Eunja and Weck, Philippe and Poineau, Frederic},

  abstractNote = {We present that zirconium tetrachloride, ZrCl4, is a strategic material with wide-ranging applications. Until now, only one crystallographic study on ZrCl4has been reported [Krebs (1970).Z. Anorg. Allg. Chem.378, 263–272] and that was more than 40 years ago. The compound used for the previous determination was prepared from ZrO2 and Cl2–CCl4, and single-crystal X-ray diffraction (SCXRD) studies on ZrCl4 obtained from Zr metal have not yet been reported. In this context, we prepared ZrCl4 from the reaction of Zr metal and Cl2 gas in a sealed tube and investigated its structure at 100, 150, 200, 250, and 300 K. At 300 K, the SCXRD analysis indicates that ZrCl4 crystallizes in the orthorhombic space group Pca21 [a= 6.262 (9),b= 7.402 (11),c= 12.039 (17) Å, andV= 558.0 (14) Å3] and consists of infinite zigzag chains of edge-sharing ZrCl6 octahedra. This chain motif is similar to that observed previously in ZrCl4, but the structural parameters and space group differ. Finally, in the temperature range 100–300 K, no phase transformation was identified, while elongation of intra-chain Zr...Zr [3.950 (1) Å at 100 K and 3.968 (5) Å at 300 K] and inter-chain Cl...Cl [3.630 (3) Å at 100 K and 3.687 (9) Å at 300 K] distances occurred.},

  doi          = {10.1107/S205322961800219X},

  journal      = {Acta Crystallographica. Section C, Structural Chemistry (Online)},

  number       = 3,

  volume       = 74,

  place        = {United States},

  year         = {Mon Feb 19 00:00:00 EST 2018},

  month        = {Mon Feb 19 00:00:00 EST 2018}

}

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Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

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https://doi.org/10.1107/S205322961800219X

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Citation Metrics:

Cited by: 5 works

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Figures / Tables:

Table 1: Crystal data and refinement quality factors for ZrCl₄

All figures and tables (7 total)

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Works referenced in this record:

Zirconium recovery from zircaloy shavings
journal, July 1996

Bohe, A. E.; Gamboa, J. J. Andrade; Lopasso, E. M.
Journal of Materials Science, Vol. 31, Issue 13
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Zirconium Tetrachloride
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Bora, Utpal
Synlett, Issue 7
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Process Development Studies for Zirconium Recovery/Recycle from used Nuclear Fuel Cladding
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Collins, E. D.; DelCul, G. D.; Spencer, B. B.
Procedia Chemistry, Vol. 7
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Elder, Michael; Penfold, Bruce R.
Inorganic Chemistry, Vol. 5, Issue 7
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Untersuchungen über die Zirkonerde
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Hermann, B.
Journal für Praktische Chemie, Vol. 31, Issue 1
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Technetium Tetrachloride Revisited: A Precursor to Lower-Valent Binary Technetium Chlorides
journal, July 2012

Johnstone, Erik V.; Poineau, Frederic; Forster, Paul M.
Inorganic Chemistry, Vol. 51, Issue 15
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Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination
journal, January 2015

Krause, Lennard; Herbst-Irmer, Regine; Sheldrick, George M.
Journal of Applied Crystallography, Vol. 48, Issue 1
DOI: 10.1107/S1600576714022985

The Crystal Structure of Zirconium(IV) Chloride: A New AB4-type Structure
journal, February 1969

Krebs, B.
Angewandte Chemie International Edition in English, Vol. 8, Issue 2
DOI: 10.1002/anie.196901461

Die Kristallstruktur von Zirkoniumtetrachlorid
journal, December 1970

Krebs, Bernt
Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 378, Issue 3
DOI: 10.1002/zaac.19703780306

ZrCl4-catalyzed X–C/C–C bond formation for the geometric selective synthesis of (E)-β-iodo aza Morita–Baylis–Hillman (MBH) adducts
journal, October 2006

Li, Qingjiang; Shi, Min; Lyte, Joshua M.
Tetrahedron Letters, Vol. 47, Issue 44
DOI: 10.1016/j.tetlet.2006.08.128

The selective catalytic oxidation of methane to methyl bisulfate at ambient pressure
journal, December 2007

Michalkiewicz, Beata; Kosowski, Patryk
Catalysis Communications, Vol. 8, Issue 12
DOI: 10.1016/j.catcom.2007.03.014

Chlorination Reaction Behavior of Zircaloy-4 Hulls: A Preliminary Study on the Effect of the Oxidation Process on the Reaction Rate [Zircaloy-4 피복관의 염소화 반응 거동: 산화 공정이 반응 속도에 미치는 영향에 대한 기초 연구]
journal, March 2013

Jeon, Min Ku; Lee, Chang Hwa; Heo, Chul Min
Journal of the Korean Radioactive Waste Society, Vol. 11, Issue 1
DOI: 10.7733/jkrws.2013.11.1.69

Use of intensity quotients and differences in absolute structure refinement
journal, May 2013

Parsons, Simon; Flack, Howard D.; Wagner, Trixie
Acta Crystallographica Section B Structural Science Crystal Engineering and Materials, Vol. 69, Issue 3
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Crystal structure of platinum tetrachloride
journal, January 1972

Pilbrow, M. F.
Journal of the Chemical Society, Chemical Communications, Issue 5
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Chemical vapor deposited borides of the form (Ti,Zr)B2 and (Ta,Ti)B2
journal, November 1979

Randich, E.
Thin Solid Films, Vol. 63, Issue 2
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Raman spectroscopy study of products of reactions of zirconium and hafnium tetrachlorides with indium and thallium monochlorides
journal, May 2013

Salyulev, A. B.; Vovkotrub, E. G.
Russian Journal of Applied Chemistry, Vol. 86, Issue 5
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Zirconium(IV) Chloride Catalyzed New and Efficient Protocol for the Selective Cleavage of p -Methoxybenzyl Ethers
journal, May 2003

Sharma, Gangavaram V. Madhava; Reddy, Ch Govardhan; Krishna, Palakodety Radha
The Journal of Organic Chemistry, Vol. 68, Issue 11
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SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

Sheldrick, George M.
Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
DOI: 10.1107/S2053273314026370

Crystal structure refinement with SHELXL
journal, January 2015

Sheldrick, George M.
Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
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Die Schwingungsspektren von ZrCl4 und Zr(NO3)4
journal, March 1968

Weidlein, J.; Müller, U.; Dehnicke, K.
Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 24, Issue 3
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Figures / Tables found in this record:

Table 3: Con't (p. 6)

Table 4 (p. 8)

Table 5 (p. 8)

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

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The bis(tetraphenylarsonium) hexachloridozirconate(IV) salt, (AsPh ₄ ) ₂ [ZrCl ₆ ] (Ph = C ₆ H ₅ ), was prepared more than 25 years ago [Esmadi & Sutcliffe (1991). Indian J. Chem. 30 A , 99–101], but its crystal structure was never reported. By following a similar experimental procedure, the compound was synthesized and its crystal structure was investigated as a acetonitrile tetrasolvate, (As(C ₆ H ₅ ) ₄ ) ₂ [ZrCl ₆ ]·4CH ₃ CN, by single-crystal X –ray diffraction. The [ZrCl ₆ ] ²⁻ anion adopts a slightly distorted octahedral coordination sphere, with Zr—Cl bond lengths of 2.4586 (6), 2.4723 (6),more »« less
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The goal of this work is to investigate the thermochemistry of used fuel Zr cladding component chlorides as well as their activation products and residual radionuclide metal chlorides, in order to provide the DOE-NE community with fundamental data that will support the development of a chlorination process for the separation and purification of ZrCl₄. Our studies will focus on the following elements: Zr, Sn, Fe, Cr, Sb, Nb and Cs; in the following sections, the term “chloride species” is applied to the following elements: Sn, Fe, Cr, Sb, Nb and Cs. Experimental and theoretical research will focus on the characterization,more »« less
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Full Text Available
THE HEATS OF FORMATION OF METAL HALIDES. ZIRCONIUM TETRACHLORIDE

Journal Article Gross, P ; Hayman, C ; Levi, D L - Transactions of the Faraday Society (England) Superseded by J. Chem. Soc., Faraday Trans., I and II

In order to determine the heat of formation of ZrCl/sub 4/, the heat evolved in the reaction Zr (s) + 2 Cl/sub 2/ (l) yields ZrCl/sub 4/(s) has been measured. The derived heat of formation of ZrCl/sub 4/ from Zr and liquid Cl is --225.89 kcal/mole, leading to a value of --234.7 kcal/mole for the standard heat of formation. The heat of interaction between Cl and ZrCl/sub 4/ was shown to be negligible. (auth)
https://doi.org/10.1039/tf9575301285
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The title compounds are obtained in high yield by reaction of stoichiometric quantities of ZrCl/sub 4/, KCl, powdered Zr, and the interstitial element B or Be in sealed tantalum containers at 800-850/sup 0/C for 2-3 weeks. The structures were established by single-crystal means to be orthorhombic for K/sub 2/Zr/sub 6/Cl/sub 15/B (Cccm, Z = 4, R = 3.3, R/sub w/ = 4.1) and monoclinic for K/sub 3/Zr/sub 6/Cl/sub 15/Be (C2/c, Z = 4, R = 4.8, R/sub w/ = 3.2). Both contain crisscrossing linear chains of trans-bridged clusters ...(Zr/sub 6/Cl/sub 12/B(Be))-Cl/sup a-a/... that are further interconnected by bent Cl/sup a-a/more »« less
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Title: Zirconium tetrachloride revisited

Abstract

Citation Formats

Figures / Tables:

Zirconium recovery from zircaloy shavings journal, July 1996

Zirconium Tetrachloride journal, January 2003

Process Development Studies for Zirconium Recovery/Recycle from used Nuclear Fuel Cladding journal, January 2012

The Crystal Structure of Technetium (IV) Chloride. A New AB 4 Structure journal, July 1966

Untersuchungen über die Zirkonerde journal, January 1844

Technetium Tetrachloride Revisited: A Precursor to Lower-Valent Binary Technetium Chlorides journal, July 2012

Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination journal, January 2015

The Crystal Structure of Zirconium(IV) Chloride: A New AB4-type Structure journal, February 1969

Die Kristallstruktur von Zirkoniumtetrachlorid journal, December 1970

ZrCl4-catalyzed X–C/C–C bond formation for the geometric selective synthesis of (E)-β-iodo aza Morita–Baylis–Hillman (MBH) adducts journal, October 2006

The selective catalytic oxidation of methane to methyl bisulfate at ambient pressure journal, December 2007

Chlorination Reaction Behavior of Zircaloy-4 Hulls: A Preliminary Study on the Effect of the Oxidation Process on the Reaction Rate [Zircaloy-4 피복관의 염소화 반응 거동: 산화 공정이 반응 속도에 미치는 영향에 대한 기초 연구] journal, March 2013

Use of intensity quotients and differences in absolute structure refinement journal, May 2013

Crystal structure of platinum tetrachloride journal, January 1972

Chemical vapor deposited borides of the form (Ti,Zr)B2 and (Ta,Ti)B2 journal, November 1979

Raman spectroscopy study of products of reactions of zirconium and hafnium tetrachlorides with indium and thallium monochlorides journal, May 2013

Zirconium(IV) Chloride Catalyzed New and Efficient Protocol for the Selective Cleavage of p -Methoxybenzyl Ethers journal, May 2003

SHELXT – Integrated space-group and crystal-structure determination journal, January 2015

Crystal structure refinement with SHELXL journal, January 2015

Die Schwingungsspektren von ZrCl4 und Zr(NO3)4 journal, March 1968

Zirconium recovery from zircaloy shavings
journal, July 1996

Zirconium Tetrachloride
journal, January 2003

Process Development Studies for Zirconium Recovery/Recycle from used Nuclear Fuel Cladding
journal, January 2012

The Crystal Structure of Technetium (IV) Chloride. A New AB ₄ Structure
journal, July 1966

Untersuchungen über die Zirkonerde
journal, January 1844

Technetium Tetrachloride Revisited: A Precursor to Lower-Valent Binary Technetium Chlorides
journal, July 2012

Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination
journal, January 2015

The Crystal Structure of Zirconium(IV) Chloride: A New AB4-type Structure
journal, February 1969

Die Kristallstruktur von Zirkoniumtetrachlorid
journal, December 1970

ZrCl4-catalyzed X–C/C–C bond formation for the geometric selective synthesis of (E)-β-iodo aza Morita–Baylis–Hillman (MBH) adducts
journal, October 2006

The selective catalytic oxidation of methane to methyl bisulfate at ambient pressure
journal, December 2007

Chlorination Reaction Behavior of Zircaloy-4 Hulls: A Preliminary Study on the Effect of the Oxidation Process on the Reaction Rate [Zircaloy-4 피복관의 염소화 반응 거동: 산화 공정이 반응 속도에 미치는 영향에 대한 기초 연구]
journal, March 2013

Use of intensity quotients and differences in absolute structure refinement
journal, May 2013

Crystal structure of platinum tetrachloride
journal, January 1972

Chemical vapor deposited borides of the form (Ti,Zr)B2 and (Ta,Ti)B2
journal, November 1979

Raman spectroscopy study of products of reactions of zirconium and hafnium tetrachlorides with indium and thallium monochlorides
journal, May 2013

Zirconium(IV) Chloride Catalyzed New and Efficient Protocol for the Selective Cleavage of p -Methoxybenzyl Ethers
journal, May 2003

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

Crystal structure refinement with SHELXL
journal, January 2015

Die Schwingungsspektren von ZrCl4 und Zr(NO3)4
journal, March 1968