Abstract
AbstractIsotope fractionation of Zn was studied via liquid‐liquid extraction with aqueous phase of ZnCl2/HCl and organic phase of crown ethers(CEs), including benzo15‐crown‐5(B15C5), benzo‐18‐crown‐6(B18C6) and Dicyclohexano‐24‐crown‐8(DC24C8)/1,2‐ dichloroethane. The isotope enrichment factor (ϵ66), expressed in permil notation, of the isotope pair 66Zn−64Zn was found to be between −0.24 and −0.52 ‰ in the order of enrichment: B15C5≥B18C6>DC24C8. The magnitude of ϵ66was well explained by theoretical isotope fractionation factors obtained by density functional theory method for zinc chloride and ZnCl2/CE model molecules, and a thermochemical description that correlates ϵ66 with the differences in Gibbs free energy(ΔG) of the exchange reaction, here termed δΔG, based on the mass differences of Zn isotopes involved. Finally, results suggest that ϵ66 may be used as a diagnostic and metric of Zn metabolic derangement, such as in porphyrias.
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