Synthesis and characterization of oxide interstitial derivatives of zirconium monochloride and monobromide

dc.contributor.author Seaverson, Linda
dc.contributor.department Chemistry
dc.date 2018-08-16T05:27:02.000
dc.date.accessioned 2020-07-02T06:10:18Z
dc.date.available 2020-07-02T06:10:18Z
dc.date.copyright Fri Jan 01 00:00:00 UTC 1982
dc.date.issued 1982
dc.description.abstract <p>An investigation into the reactivity of ArX (X = Br,Cl) found no evidence for successful intercalation of ZrCl between the chloride layers with NH(,3(g)) (up to 300(DEGREES)C), pyridine (190(DEGREES)), CO(,(g)) (170(DEGREES)), n-butyl lithium (25(DEGREES), 60(DEGREES)), Li/NH(,3) (-33 to -78(DEGREES)), K/NH(,3) (-33 to -78(DEGREES)), and Li (850(DEGREES)); and Zr plus LiCl (700(DEGREES)), CsCl (780(DEGREES)), and NaCl (930(DEGREES));Reactions of ZrX + n ZrO(,2) under isothermal conditions at 850-1000(DEGREES) for two weeks in welded tantalum containers produced an expanded ZrX structure (ZrX(O(,y))) and the metal phase Zr(O(,x))(X(,p)) (p (TURNEQ) 0). For ZrCl(O(,y)) saturation occurred at n = 0.27 (+OR-) 0.01 where the average cell dimensions are a = 3.4956(5) and c = 27.06(1) (ANGSTROM) (Guinier data) (a = 3.433(5), c = 26.693(3) (ANGSTROM) for ZrCl). For ZrBr(O(,y)), saturation occurred at n = 0.22 (+OR-) 0.02 where the average dimensions are a = 3.5584(4) and c = 28.430(7) (ANGSTROM) (a = 3.5064(2), c = 28.068(2) (ANGSTROM) for ZrBr);The a lattice dimensions of the metal phase from both halide systems were found to vary similarly to that of Zr(O(,x)) with increased oxide with the latter always 0.005 (ANGSTROM) larger. The a lattice dimension at saturation is in reasonable agreement to those cited above for ZrX(O(,y)). The c dimension of this phase saturated at a much lower oxide level with a noticeable increase of the bromide value (a = 3.239(2), c = 5.2189(9) (ANGSTROM)) over the chloride value (a = 3.2398(4), 5.2077(7) (ANGSTROM)), indicating possible halide incorporation although only a minute amount could be detected by electron microprobe;Three ZrCl(O(,y)) crystal structures were refined, y = 0.25(5), 0.29(4), and 0.43(2). One ZrBr(O(,y)) structure was partially refined. The oxide is incorporated into the tetrahedral-like interstices between the zirconium layers with no X-ray evidence of ordering. The ZrX structures with layers sequenced X-Zr-Zr-X do not change stacking order (ABCA for ZrCl and ACBA for ZrBr) or symmetry (R(')3M) with the addition of oxygen. ZrCl(O(,0.43(2))) represents the composition at saturation and has intralayer d(Zr-Zr = d(O-O) = d(Cl-Cl) = 3.4984(2) (ANGSTROM); and interlayer d(Zr-Zr) = 3.199(2) (ANGSTROM), d(Cl-Cl) = 3.648(5) (ANGSTROM), d(O-O) = 2.71(3) (ANGSTROM), d(Zr-Cl) = 2.673(2) (ANGSTROM), d(Zr(,apex)-O) = 2.15(2) (ANGSTROM), d(Zr(,base)-O) = 2.047(3) (ANGSTROM);The above information leads to the balanced equations at saturation ZrCl(s) + 0.27 ZrO(,2)(s) (--->) ZrCl(O(,0.43))(s) + 0.27 Zr(O(,0.42))(s) and ZrBr(s) + 0.22 ZrO(,2)(s) (--->) ZrBr(O(,0.35))(s) + 0.22 Zr(O(,0.42))(s); *DOE Report IS-T-1036. This work was performed under Contract No. W-7405-Eng-82 with the U.S. Department of Energy.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/8958/
dc.identifier.articleid 9957
dc.identifier.contextkey 6347471
dc.identifier.doi https://doi.org/10.31274/rtd-180813-11345
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/8958
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/82003
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/8958/r_8407122.pdf|||Sat Jan 15 02:19:33 UTC 2022
dc.subject.disciplines Inorganic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Inorganic chemistry
dc.title Synthesis and characterization of oxide interstitial derivatives of zirconium monochloride and monobromide
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
thesis.degree.level dissertation
thesis.degree.name Doctor of Philosophy
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