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Solution Thermodynamics for the Thorium Complexation with N-(2-Hydroxyethyl) Iminodiacetic Acid
Journal of Chemical & Engineering Data ( IF 2.0 ) Pub Date : 2020-05-18 , DOI: 10.1021/acs.jced.9b00798 Shikha Sharma 1 , Rama Mohana Rao Dumpala 1 , Neetika Rawat 1
Journal of Chemical & Engineering Data ( IF 2.0 ) Pub Date : 2020-05-18 , DOI: 10.1021/acs.jced.9b00798 Shikha Sharma 1 , Rama Mohana Rao Dumpala 1 , Neetika Rawat 1
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N-(2-Hydroxyethyl)iminodiacetic acid (HEIDA-H2) is one of the major chelating agents present in the mixed nuclear waste of the Hanford site. The complexation of thorium with HEIDA-H2 in aqueous medium was investigated to understand the capability of HEIDA-H2 to affect the migration of actinides from the waste storage sites. The present studies aimed at determining the thermodynamic parameters of Th(IV)–HEIDA complexes to know the speciation, stability (log K) and strength of bond formations (enthalpy and entropy changes) by potentiometric and calorimetric titrations, respectively. Thorium forms ML, ML2 and ML3 complexes with HEIDA. The obtained log K values 11.25 ± 0.10, 9.24 ± 0.10, and 8.1 ± 0.10, are higher than the complexes of thorium with monodenatate ligands (simple carboxylates), bidentate ligands (aminomonocarboxylates, dicarboxylates), and heterodicarboxylates. The very high entropy values of the Th(IV)–HEIDA complexes in comparison to the Th(IV) complexes with structurally similar ligands reflects the stronger complexation of Th with HEIDA over others. HEIDA acts as a tridentate ligand forming two five-membered chelates through the two carboxylate oxygens and the nitrogen with thorium, while the hydroxyethl group was found to enhance the stabilization by indirect participation. Density functional theory was used to optimize the geometries and to determine the thermodynamic parameters, bond distances and partial charges on individual atoms for the experimentally predicted complexes. The theoretical predictions are found to be in agreement with the experimental observations.
中文翻译：
ium与N-（2-羟乙基）亚氨基二乙酸络合的溶液热力学
N-（2-羟乙基）亚氨基二乙酸（HEIDA-H 2）是存在于汉福德基地混合核废料中的主要螯合剂之一。研究了or与HEIDA-H 2在水性介质中的络合作用，以了解HEIDA-H 2影响affect系元素从废物储存地点迁移的能力。本研究旨在确定Th（IV）-HEIDA配合物的热力学参数，以分别通过电位滴定法和量热法滴定法来了解形态，稳定性（log K）和键形成强度（焓和熵变）。ium与HEIDA形成ML，ML 2和ML 3配合物。获得的日志K11.25±0.10、9.24±0.10和8.1±0.10的值要高于th与单denateate配体（简单的羧酸盐），双齿配体（氨基单羧酸盐，二羧酸盐）和杂二羧酸盐的配合物。与具有相似结构配体的Th（IV）配合物相比，Th（IV）–HEIDA配合物的熵值非常高，这反映了Th与HEIDA的配合力强于其他配合物。HEIDA充当三齿配体，通过两个羧酸氧和氮与th形成两个五元螯合物，而羟乙基则通过间接参与而增强了稳定性。密度泛函理论用于优化几何形状，并确定实验预测的配合物的单个原子上的热力学参数，键距和部分电荷。
更新日期：2020-05-18
中文翻译：
ium与N-（2-羟乙基）亚氨基二乙酸络合的溶液热力学
N-（2-羟乙基）亚氨基二乙酸（HEIDA-H 2）是存在于汉福德基地混合核废料中的主要螯合剂之一。研究了or与HEIDA-H 2在水性介质中的络合作用，以了解HEIDA-H 2影响affect系元素从废物储存地点迁移的能力。本研究旨在确定Th（IV）-HEIDA配合物的热力学参数，以分别通过电位滴定法和量热法滴定法来了解形态，稳定性（log K）和键形成强度（焓和熵变）。ium与HEIDA形成ML，ML 2和ML 3配合物。获得的日志K11.25±0.10、9.24±0.10和8.1±0.10的值要高于th与单denateate配体（简单的羧酸盐），双齿配体（氨基单羧酸盐，二羧酸盐）和杂二羧酸盐的配合物。与具有相似结构配体的Th（IV）配合物相比，Th（IV）–HEIDA配合物的熵值非常高，这反映了Th与HEIDA的配合力强于其他配合物。HEIDA充当三齿配体，通过两个羧酸氧和氮与th形成两个五元螯合物，而羟乙基则通过间接参与而增强了稳定性。密度泛函理论用于优化几何形状，并确定实验预测的配合物的单个原子上的热力学参数，键距和部分电荷。
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