镧系六氟乙酰丙酮螯合物的表征及热重分析

Characterization and thermogravimetric analysis of lanthanide hexafluoroacetylacetone chelates.

作者信息

Shahbazi Shayan, Stratz S Adam, Auxier John D, Hanson Daniel E, Marsh Matthew L, Hall Howard L

机构信息

Department of Nuclear Engineering, University of Tennessee, 301 Middle Dr., Pasqua Nuclear Engineering Building, Knoxville, TN 37996 USA.

Department of Nuclear Engineering, University of Tennessee, 301 Middle Dr., Pasqua Nuclear Engineering Building, Knoxville, TN 37996 USA ; Radiochemistry Center of Excellence, University of Tennessee, 1508 Middle Dr., Ferris Hall, Knoxville, TN 37996 USA ; Institute for Nuclear Security, University of Tennessee, 1640 Cumberland Ave. Howard Baker Jr. Center for Public Policy, Knoxville, TN 37996 USA.

出版信息

J Radioanal Nucl Chem. 2017;311(1):617-626. doi: 10.1007/s10967-016-5005-0. Epub 2016 Aug 30.

DOI:10.1007/s10967-016-5005-0

PMID:28111487

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5219043/

Abstract

This work reports the thermodynamic characterizations of organometallic species as a vehicle for the rapid separation of volatile nuclear fission products via gas chromatography due to differences in adsorption enthalpy. Because adsorption and sublimation thermodynamics are linearly correlated, there is considerable motivation to determine sublimation enthalpies. A method of isothermal thermogravimetric analysis, TGA-MS and melting point analysis are employed on thirteen lanthanide 1,1,1,5,5,5-hexafluoroacetylacetone complexes to determine sublimation enthalpies. An empirical correlation is used to estimate adsorption enthalpies of lanthanide complexes on a quartz column from the sublimation data. Additionally, four chelates are characterized by SC-XRD, elemental analysis, FTIR and NMR.

摘要

这项工作报道了有机金属物种的热力学特性，作为一种通过气相色谱法快速分离挥发性核裂变产物的媒介，这是由于吸附焓的差异所致。由于吸附和升华热力学呈线性相关，因此有很大的动力去测定升华焓。采用等温热重分析、热重-质谱联用和熔点分析方法，对13种镧系1,1,1,5,5,5-六氟乙酰丙酮配合物进行了测定，以确定升华焓。利用经验关联式，根据升华数据估算镧系配合物在石英柱上的吸附焓。此外，通过单晶X射线衍射、元素分析、傅里叶变换红外光谱和核磁共振对四种螯合物进行了表征。