title: Experimental and theoretical investigation of isotope fractionation of zinc between aqua, chloro, and macrocyclic complexes.
abstract: This work reports on the chemical isotope fractionation of Zn(II) by a solvent extraction method with the crown ether dicyclohexano-18-crown-6. The (m)Zn/(64)Zn ratios (m = 66, 67, and 68) were analyzed by multiple-collector inductively coupled plasma mass spectrometry. The relative deviations of the (66)Zn/(64)Zn ratios relative to the unprocessed material (delta(66)Zn) was determined to be -0.51 to -0.32 in the acidity region 1.0-6.0 mol dm(-3) (M) HCl. The acidity dependence of delta(m)Zn was explained by the isotope exchange reactions between Zn(II) species (Zn(2+), ZnCl(+), ZnCl(2), ZnCl(3)(-), and ZnCl(4)(2-)) and the mole fractions of them. The magnitude of delta(m)Zn due to the related Zn(II) species estimated by quantum chemical calculations was in agreement with delta(m)Zn experimentally obtained. Contribution of nuclear field shift to the isotope fractionation was estimated to be less than 10% of delta(m)Zn by quantum chemical calculations.
authors.affiliation: Research Reactor Institute, Kyoto University, 2-1010 Asashiro Nishi, Kumatori, Sennan Osaka 590-0494, Japan. tosiyuki@rri.kyoto-u.ac.jp
authors.forename: Toshiyuki
authors.initials: T
authors.lastname: Fujii
authors.forename: Frédéric
authors.initials: F
authors.lastname: Moynier
authors.forename: Philippe
authors.initials: P
authors.lastname: Telouk
authors.forename: Minori
authors.initials: M
authors.lastname: Abe
mesh_terms: D003198:Computer Simulation; D043844:Crown Ethers / Q000737:chemistry*; D006851:Hydrochloric Acid / Q000737:chemistry*; D047028:Macrocyclic Compounds / Q000737:chemistry*; D013058:Mass Spectrometry; D011789:Quantum Theory; D015032:Zinc / Q000737:chemistry*; D015033:Zinc Isotopes / Q000737:chemistry
chemical_list: D043844:Crown Ethers; D047028:Macrocyclic Compounds; D015033:Zinc Isotopes; C002570:dicyclohexyl-18-crown-6; D015032:Zinc; D006851:Hydrochloric Acid