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Thorium(IV) chloride
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<h2 id="structures">Structures</h2> <p>The structure of thorium(IV) chloride features 8-coordinate Th centers with doubly bridging chloride ligands.<a class="footnote-ref" id="fnref:1" href="#fn:1"><sup>1</sup></a> </p> <h2 id="synthesis">Synthesis</h2> <p>ThCl4 was an intermediate in the original isolation of thorium metal by <a href="/facts/J%25C3%25B6ns_Jacob_Berzelius/HakSv3sP">Jons Jacob Berzelius</a>.<a class="footnote-ref" id="fnref:2" href="#fn:2"><sup>2</sup></a> </p><p>Thorium(IV) chloride can be produced in a variety of ways. One method is a <a href="/facts/Carbothermic_reaction/gj0GA25m">carbothermic reaction</a>, 700 °C to 2600 °C, involving thorium oxides and carbon in a stream of chlorine gas: </p> ThO2 + 2 C + 4 Cl2 → ThCl4 + 2 CO <p>The chlorination reaction can be effected with carbon tetrachloride:<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a><a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> </p> Th(C2O4)2 + CCl4 → ThCl4 + 3 CO + 3 CO2 <p>In another two-step method, thorium metal reacts with <a href="/facts/Ammonium_chloride/SfXdntlv">ammonium chloride</a>: </p> Th + 6 NH4Cl → (NH4)2ThCl6 + 4 NH3 + 2 H2 <p>The hexachloride salt is then heated at 350 °C under a high vacuum to produce ThCl4.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> </p> <h2 id="reactions">Reactions</h2> Lewis base adducts <p>ThCl4 reacts with <a href="/facts/Lewis_base/qlLqRvg2">Lewis bases</a> to give molecular adducts, such as ThCl4(DME)2 and ThCl4(TMEDA)2.<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> </p> Reduction to Th metal <p>Thorium(IV) chloride is an intermediate in the purification of thorium, which can be affected by: </p> <ol><li>Reduction of ThCl4 with alkali metals.</li> <li>Electrolysis of anhydrous thorium(IV) chloride in fused mixture of NaCl and KCl.</li> <li>Ca reduction of a mixture of ThCl4 with anhydrous zinc chloride.<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a></li></ol> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Mason, J. T.; Jha, M. C.; Chiotti, P. (1974). "Crystal Structures of ThCl4 Polymorphs". Journal of the Less Common Metals. 34: 143–151. doi:10.1016/0022-5088(74)90224-0. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Weeks, Mary Elvira (1932-07-01). "The Discovery of the Elements. XI. Some Elements Isolated with the Aid of Potassium and Sodium: Zirconium, Titanium, Cerium, and Thorium". Journal of Chemical Education. 9 (7): 1231. Bibcode:1932JChEd...9.1231W. doi:10.1021/ed009p1231. ISSN 0021-9584. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Brauer, Georg (1963). Handbook Of Preparative Inorganic Chemistry. New York: Academic Press. <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Gutierrez, R. L.; Herbst, R. J. (October 1979). "Preliminary Fabrication Studies of Alternative LMFBR Carbide Fuels". Los Alamos Scientific Laboratory. doi:10.2172/5688597. <a href="https://www.osti.gov/scitech/servlets/purl/5688597-2bGijb/" target="_blank">https://www.osti.gov/scitech/servlets/purl/5688597-2bGijb/</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>Cantat, Thibault; Scott, Brian L.; Kiplinger, Jaqueline L. (2010-01-25). "Convenient Access to the Anhydrous Thorium Tetrachloride Complexes ThCl4(DME)2, ThCl4(1,4-dioxane)2 and ThCl4(THF)3.5 using Commercially Available and Inexpensive Starting Materials". Chemical Communications. 46 (6): 919–21. doi:10.1039/b923558b. ISSN 1364-548X. PMID 20107650. <a href="https://zenodo.org/record/1229998" target="_blank">https://zenodo.org/record/1229998</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Cantat, Thibault; Scott, Brian L.; Kiplinger, Jaqueline L. (2010-01-25). "Convenient Access to the Anhydrous Thorium Tetrachloride Complexes ThCl4(DME)2, ThCl4(1,4-dioxane)2 and ThCl4(THF)3.5 using Commercially Available and Inexpensive Starting Materials". Chemical Communications. 46 (6): 919–21. doi:10.1039/b923558b. ISSN 1364-548X. PMID 20107650. <a href="https://zenodo.org/record/1229998" target="_blank">https://zenodo.org/record/1229998</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>"Periodic Table of Elements: Los Alamos National Laboratory". periodic.lanl.gov. Retrieved 2016-04-29. <a href="http://periodic.lanl.gov/90.shtml" target="_blank">http://periodic.lanl.gov/90.shtml</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> </ol>