Temperature Fractionation (TF) of Hg Compounds in Gypsum from Wet Flue Gas Desulfurization System of the Coal Fired Thermal Power Plant (TPP)

Gypsum from the wet flue gas desulfurization system of the lignite fired thermal power plant Sostanj, Slovenia, can efficiently retain mercury (Hg), of which most is contained in finer gypsum fractions, with concentrations above 10 kg-1. The aim of this work was to identify and study the temperature stability of Hg species in gypsum by a temperature fractionation (TF) method. A self-constructed apparatus was used that consisted of an electrical furnace for controlled heating up to 700°C, with a heating rate of 2.2°C·min-1, and an AAS detector with Zeeman background correction. The pattern of Hg release during temperature increase depends highly on the matrix/substrate in which it is contained. Based on spiking gypsum with known Hg compounds we concluded that the largest proportion of Hg in gypsum belongs to Hg-Cl and Hg-Br compounds appearing at 160°C to 200°C, followed by smaller amounts of HgO, HgS and Hg sulfates appearing at 300°C and 450°C. Further development of methodology for identifying Hg species would require identification of the decomposition fragments of Hg and other compounds, complemented by a better understanding of Hg reactivity at higher temperatures.

Syntheses and Crystal Structures of Two New Mercury(Ⅱ) Complexes with Double Betaine Ligands

Reaction of HgCl2 and double betaine ligands in water at about 80 ℃ yielded two new Hg（Ⅱ） complexes,[Hg（L1）Cl2]·H2O 1 and [Hg2（L2）Cl4]·3HgCl2 2（L1 = 1,3-bis（pyridinio-4-carboxylato）-propane,L2 = 1,4-bis（pyridinio-4-carboxylato）-1,4-dimenthylbenzene）.Their struc-tures have been characterized by single-crystal X-ray diffraction techniques.The structure of 1 contains 1-D chains,in which the adjacent Hg（Ⅱ） atoms are bridged by L1 ligands in a syn-syn bis-monodentate mode.The chains are further connected through face-to-face π-π stacking interactions between pyridine rings to generate an infinite double-chain network.In 2,two Hg（Ⅱ） atoms are joined by L2 ligands in the same coordination mode as 1 to form an isolated dinuclear structure.The thermal stabilities of both complexes have also been investigated.

Syntheses and Crystal Structures of Two New Supramolecular Architectures Constructed from the Main Group Metal Chloride and Protonated 2-(3-Pyridyl)benzimidazole

The reactions of SbCl3 and HgCl2 with 2-（3-pyridyl）benzimidazole （PyBIm） in solution acidified with HCl have been investigated. The PyBIm ligands are protonated into 2-（3-pyridinio）benzimidazolium （H2PyBIm） cations and the corresponding metal ions are bonded with chloride atoms into coordination anions, forming two new coordination compounds, namely, （H2PyBIm）（SbCl5） 1 and （H2PyBIm）2（Hg2Cl8） 2. Both compounds were characterized by X-ray crystallography. Crystal data for 1： triclinic, space group P1^- with a = 5.7030（7）, b = 9.0625（11）, c = 16.5929（18） A, α = 91.808（7）°, β = 93.234（6）, γ = 99.216（7）°, C12H11N3SbCl5, Mr = 496.24, V = 844.44（17） A^3, Z = 2, Dc = 1.952 g/cm^3, μ（MoKα） = 2.419 mm^-1, F（000） = 480, the final R = 0.0496 and wR = 0.1382 for 3433 observed reflections （I 〉 2σ（I））. Crystal data for 2： monoclinic, space group P21/c with a = 7.8061（5）, b = 15.8127（9）, c = 12.2435（9） , β = 91.955（4）o, C24H22N6Hg2Cl8, Mr = 1079.26, V = 1510.40（17） 3, Z = 2, Dc = 2.373 g/cm3, μ（MoKα） = 10.889 mm-1, F（000） = 1008, the final R = 0.0293 and wR = 0.0562 for 2854 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that the antimony（III） is five-coordinated, exhibiting a slightly distorted square-pyramidal coordination geometry; while in 2, a dimeric [Hg2Cl8]^4-anion consists of two trigonal bipyramids sharing two common edges. The organic cations and coordination anions are connected into a one-dimensional belt and a two-dimensional sheet through N-H···Cl hydrogen bonding interactions in compounds 1 and 2, respectively; both are further aggregated into 3D frameworks by strong π-π contacts.