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Zirconium Chloride Molecular Species: Combining Electron Impact Mass Spectrometry and First Principles Calculations

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Zirconium Chloride Molecular Species: Combining Electron Impact Mass Spectrometry and First Principles Calculations Research Article Zirconium chloride molecular species: combining electron impact mass spectrometry and frst principles calculations Rosendo Borjas Nevarez1 · Eunja Kim2 · Bradley C. Childs3 · Henrik Braband3 · Laurent Bigler3 · Urs Stalder3 · Roger Alberto3 · Philippe F. Weck4 · Frederic Poineau1 © Springer Nature Switzerland AG 2019 Abstract Zirconium tetrachloride was synthesized from the reaction between zirconium metal and chlorine gas at 300 °C and was analyzed by electron impact mass spectrometry (EI-MS). Substantial fragmentation products of ZrCl4 were observed in the mass spectra, with ZrCl3 being the most abundant species, followed by ZrCl2, ZrCl, and Zr. The predicted geometry and kinetic stability of the fragments previously mentioned were investigated by density functional theory (DFT) calcu- lations. Energetics of the dissociation processes support the most stable fragment to be ZrCl3 while the least abundant are ZrCl and ZrCl2. Keywords Zirconium · Chloride · Mass spectrometry · Gas phase · DFT 1 Introduction [7], followed by ZrCl4 [8, 9]. Therefore, an accurate knowl- edge of zirconium chlorides is crucial for efcient separa- Zirconium chloride is of crucial importance in numerous tion and selective recovery of Zr from cladding materials. research felds and industrial applications such as uncon- While much attention has been given to the theoretical ventional catalysis [1], refning of Zr-containing ores by and experimental investigations of crystalline ZrCl 4 [9], Kroll reduction [2], chemical vapor deposition [3], and accurate structural and thermomechanical information nuclear engineering [4–6]. Chlorination has been pro- of ZrClx (x = 1, 2, 3, 4) molecular species remains scarce. posed for large-scale separation and selective recovery of Due to their chemical similarities and the importance of Zr as ZrCl4 from U–Zr alloys or used nuclear fuel cladding the refnement process in the nuclear industry, studies on [4, 5]. Due to the presence of impurities (e.g., Sn, Cr, Fe, gaseous ZrCl4 are typically performed in conjunction with etc.) in the recovered ZrCl 4, further eforts are necessary HfCl4. The frst electronographic approximations calculated to improve the purifcation process. This requires funda- the theoretical intensity curves based on the intermolecu- mental understanding of the materials during each stage lar distances in ZrCl4 (i.e. Zr–Cl = 2.32 Å and Cl···Cl = 3.79 Å) of the process. Starting materials consist of Zr cladding and in HfCl4 (i.e. Hf–Cl = 2.33 Å and Cl···Cl = 3.80 Å) [10]. such as Zircaloy-4, Zircaloy-2 and Zr–Nb alloys (Zirlo™ Recently, Barnes et al. reported that the vapor pressure and Zr-2.5Nb) while the fnal product should be Zr metal. of ZrCl4, FeCl3, CrCl4, NbCl5, and NbOCl3 are very similar at In the chlorination process, the intermediate material is temperatures near 330 °C [11]. The vapor pressure of ZrCl4 ZrCl4. Our previous eforts have been devoted on funda- has also been measured under vacuum and under argon mental studies of the starting materials described above atmospheres [12]. In addition, DFT models have been used * Rosendo Borjas Nevarez, [email protected] | 1Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy, Las Vegas, NV 89154, USA. 2Department of Physics and Astronomy, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy, Las Vegas, NV 89154, USA. 3Department of Chemistry, University of Zurich, Rämistrasse 71, 8006 Zurich, Switzerland. 4Sandia National Laboratories, Albuquerque, NM 87185, USA. SN Applied Sciences (2019) 1:392 | https://doi.org/10.1007/s42452-019-0410-y Received: 11 January 2019 / Accepted: 25 March 2019 / Published online: 2 April 2019 Vol.:(0123456789) Research Article SN Applied Sciences (2019) 1:392 | https://doi.org/10.1007/s42452-019-0410-y to predict the volatility and adsorption enthalpies of ZrCl4, Perfuorokerosene (PFK, Fluorochem, Derbyshire, UK) was 2− ZrOCl2, and ZrCl6 salts in comparison to the other Group used for mass calibration. IV metal chlorides. These models are for the most part in disagreement with experimental data [13], demonstrat- 2.3 Computational method ing the complexity of these gas phase interactions. As for gaseous ZrCl2, the structure, vibrational frequencies, and First-principles all-electron calculations of the total ener- heat of formation have been predicted, and they are in gies and optimized geometries were performed using the close agreement with experimental data [14]. density functional theory (DFT) as implemented in the In this study, we have carried out combined experimen- DMol3 software [15]. The exchange correlation energy was tal and computational studies to investigate the struc- calculated using the generalized gradient approximation tures, electronic properties, and relative stability of the (GGA) with the parametrization of Perdew and Wang [16] ZrClx (x = 1, 2, 3, 4) molecules in the gas phase. (PW91). Double numerical basis sets including polariza- tion functions on all atoms (DNP) were used in the calcula- tions. The DNP basis set is comparable to 6-31G** Gaussian 2 Experimental basis sets. In the generation of the numerical basis sets, a global orbital cutof of 3.7 Å was used. The energy tol- 2.1 Preparation of sample erance in the self-consistent feld calculations was set to 10−6 Hartree. Optimized geometries were obtained with- Zirconium metal sponge (> 99% purity), and a lecture bot- out symmetry constraints using an energy convergence tle of chlorine gas (> 99.5% purity) were obtained from tolerance of 10 −5 Hartree and a gradient convergence of Sigma Aldrich and used as received. The clamshell furnace 2 × 10−3 Hartree/Å. was a Lindberg Blue M Mini-Mite. ZrCl4 was synthesized from the reaction of zirconium metal and chlorine gas at 300 °C in a glass sealed tube 3 Results and discussion according to the method reported in the literature [9]. After the reaction, the end of the tube containing ZrCl 4 3.1 Electron impact mass spectrometry was placed in liquid nitrogen and the tube was sealed to separate the zirconium oxide impurity. The capillary was Zirconium chloride species yield EI-MS peaks that are rec- then checked for external contamination and sent to the ognized not only by their mass to charge ratio, but also by University of Zurich. their unique splitting pattern due to the isotopic abun- dances of Zr and Cl (Table 1). The spectrum after a reten- 2.2 Analysis of sample tion time of 6.86 min (400 °C) is presented in Fig. 1. The relative abundances of the observed species were deter- At the University of Zurich, the sealed tube was stored in mined from the sum of all the peak counts in the isotopic an inert atmosphere (N2) glove box. The tube was opened mass range. In addition to the parent ZrCl4 molecule, the in the glovebox and ZrCl4 samples were placed in sample following fragments are present in a quantifable manner: holders. The samples were then transferred to a Schlenk fask and sealed. The sample was introduced into a glove bag system, which was installed in front of the mass spec- Table 1 Splitting of a ZrCl 4 peak from m/z = 229.8 to m/z = 239.8 trometer and included the sample inlet. The system was due to isotopic abundance evacuated and then purged with argon three times before m/z Isotopic distribution opening the Schlenk fask. The ZrCl sample was mounted 4 229.8 90Zr35Cl on the probe, which was then inserted into the mass spec- 4 230.8 91Zr35Cl trometer to be measured. Mass spectrometry measure- 4 231.8 90Zr35Cl37Cl 92Zr35Cl ments were performed on a Thermo DFS (ThermoFisher 3 4 232.8 91Zr35Cl37Cl Scientifc, Bremen, Germany) double-focusing magnetic 3 233.8 92Zr35Cl37Cl 94Zr35Cl 90Zr35Cl37Cl sector mass spectrometer (geometry BE). Mass spectra 3 4 2 2 234.8 91Zr35Cl37Cl were measured in electron impact mode at 70 eV, with a 2 2 235.8 94Zr35Cl37Cl 96Zr35Cl 92Zr35Cl37Cl 90Zr35Cl37Cl solid probe inlet, source temperature of 50 °C, accelera- 3 4 2 2 2 236.8 91Zr35Cl37Cl tion voltage of 5 kV, and a resolution of 7000. The instru- 3 237.8 96Zr35Cl37Cl 94Zr35Cl37Cl 92Zr35Cl37Cl 90Zr37Cl ment was scanned from m/z = 30 to 800 at a scan rate of 2 s 3 2 2 3 4 238.8 91Zr37Cl per decade in the magnetic scan mode, and temperature 4 239.8 96Zr35Cl37Cl 94Zr35Cl37Cl 92Zr37Cl ramp rate was 60 °C per minute until 400 °C was reached. 2 2 3 4 Vol:.(1234567890) SN Applied Sciences (2019) 1:392 | https://doi.org/10.1007/s42452-019-0410-y Research Article Fig. 1 Electron impact mass spectra (70 eV) of ZrCl4 between m/z = 50 and m/z = 440 Table 2 Relative abundance of zirconium chloride fragments in the A previous EI-MS study on ZrCl4 by Schäfer detected the EI-MS spectra of ZrCl 2+ + + + + + 4 fragments: ZrCl3 , Zr , ZrCl , ZrCl2 , ZrCl3 , and Zr2Cl7 . Peak range (m/z) Molecule Intensity Abundance Also, the mass spectra revealed dimerization of ZrCl 4 to + + + (normalized) (ZrCl4)2 with a (ZrCl 4)2/ZrCl4 ratio of 0.000401 at 459 K (%) [18]. Our data supports the favorable formation of the 89.9 Zr+ 1,228,923.2 1.92 lower mass fragments. Interestingly, fragments with m/z 2+ ratios higher than the mass of ZrCl are also observed at 97.2–99.3 ZrCl3 1,836,960.4 2.87 4 124.9–128.9 ZrCl+ 5,168,760.7 8.09 m/z ~ 385 but those ratios do not agree with any of the + previous fndings or with the sum of any combination of 159.8–165.8 ZrCl2 7,295,977.8 11.4 + Zr and Cl atomic masses. 194.8–202.8 ZrCl3 25,427,641.7 39.8 + 229.8–239.8 ZrCl4 22,938,047.9 35.9 Total 63,896,311.7 100 3.2 Computational studies Systematic studies to investigate the stable geometries of + 2+ + + + ZrCl3 , ZrCl3 , ZrCl2 , ZrCl , and Zr (Table 2), with ZrCl 3 the neutral and ionic ZrCl x species has been carried out clearly as the most abundant species.
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