Interaction of the cesium cation with mono-, di-, and tricarboxylic acids in the gas phase. A Cs⁺ affinity scale for cesium carboxylates ion pairs

Abstract

Humic substances (HS), including humic and fulvic acids, play a significant role in the fate of metals in soils. The interaction of metal cations with HS occurs predominantly through the ionized (anionic) acidic functions. In the context of the effect of HS on transport of radioactive cesium isotopes in soils, a study of the interaction between the cesium cation and model carboxylic acids was undertaken. Structure and energetics of the adducts formed between Cs ϩ and cesium carboxylate salts [Cs ϩ RCOO Ϫ ] were studied by the kinetic method and density functional theory (DFT). Clusters generated by electrospray ionization mass spectrometry from mixtures of a cesium salt (nitrate, iodide, trifluoroacetate) and carboxylic acids were quantitatively studied by CID. By combining the results of the kinetic method and the energetic data from DFT calculations, a scale of cesium cation affinity, CsCA, was built for 33 cesium carboxylates representing the first scale of cation affinity of molecular salts. The structural effects on the CsCA values are discussed. (J Am Soc Mass

A study of the cesium cation bonding to carboxylate anions by the kinetic method and quantum chemical calculations

“…However, the carboxylate/phenolate ratio appears to depend somewhat on the ionization conditions (solvent, even ESI source construction). [39,40] The slope of Eqn (4) gives an effective temperature of T eff = 590 ± 20 K. This value is within the range obtained in our previous studies, carried out in an ion trap, of the dissociation of positive clusters formed with cesium salts: about 750 K for carboxylates + nitrate, iodide or trifluoroacetate, [23] 510 K for substituted benzoates + iodide. [22] The fair precision of Eqn (4) confirms that the basic conditions for the application of the kinetic method are fulfilled for the benzoate family.…”

Experimental and theoretical investigations of Cs+ adsorption on crown ethers modified magnetic adsorbent

“…Chai and Head−Gordon [23], where def2-TZVP basis set was used for the selected atoms [24,25]. Vibrational frequency calculation was used at the same level to confirm the nature of the stationary points.…”

Experimental and Computational Study of the Group 1 Metal Cation Chelates with Lysine: Bond Dissociation Energies, Structures, and Structural Trends

“…16 Radioactive 134 Cs + and 137 Cs + have also recently evolved as environmental toxins, a result of atmospheric nuclear weapons tests in the mid-19th century and following the 1986 Chernobyl 17 and 2011 Fukushima 18 accidents. Cs + readily chelates to many organic molecules, 19 including humic and fulvic acids, which are common organic acids in soil, 20 and has severe cardio pathophysiological consequences in humans exposed to those environments. 21 All five of the Group 1 metal cations Li + through Cs + are presented here to highlight binding trends to lysine.…”