CAJ | 학술논문

采用混合酸酐法合成了两种双二苷酰胺(bisdiglycolamide, BisDGA)萃取剂： N,N,N’’’,N’’’-四正辛基-N’,N″-乙二基-双二苷酰胺(TOE-BisDGA)和 N,N,N’’’,N’’’-四正辛基-N’,N″-间苯二甲基-双二苷酰胺(TOX-BisDGA).以磺化煤油和正辛醇混合溶液(体积比90：10)作稀释剂,研究了它们在硝酸溶液中对Eu(Ⅲ)和Am(Ⅲ),以及自身对 HNO3的萃取行为.结果表明,2种 BisDGAs 对 HNO3均有一定萃取,当酸度不超过1.0 mol/ L 时,二者形成1：1型的萃合物.随 HNO3浓度增加, Eu(Ⅲ)和 Am(Ⅲ)的萃取分配比增加.相同条件下, TOE-BisDGA 对 Eu(Ⅲ)和 Am(Ⅲ)的萃取能力强于 TOX-BisDGA.斜率分析表明 TOE-BisDGA 和 TOX-BisDGA 与 Eu(Ⅲ)和 Am(Ⅲ)均形成2：1型的萃合物.温度升高,萃取分配比下降,萃取反应是放热反应.2种 BisDGAs 对 Eu(Ⅲ)的亲和力强于对 Am(Ⅲ)的亲合力,表明 BisDGAs 对 Eu(Ⅲ)有一定的选择性.同时,研究了 BisDGAs 萃取 Eu(Ⅲ)和 Am(Ⅲ)的机理,给出了表观萃取平衡常数和萃取反应热力学函数△H,△S和△G 的值.此外,还对 TOE-BisDGA 和 TOX-BisDGA 与 Eu(Ⅲ)形成的配合物进行了红外和紫外光谱分析.
채용혼합산항법합성료량충쌍이감선알(bisdiglycolamide, BisDGA)췌취제： N,N,N’’’,N’’’-사정신기-N’,N″-을이기-쌍이감선알(TOE-BisDGA)화 N,N,N’’’,N’’’-사정신기-N’,N″-간분이갑기-쌍이감선알(TOX-BisDGA).이광화매유화정신순혼합용액(체적비90：10)작희석제,연구료타문재초산용액중대Eu(Ⅲ)화Am(Ⅲ),이급자신대 HNO3적췌취행위.결과표명,2충 BisDGAs 대 HNO3균유일정췌취,당산도불초과1.0 mol/ L 시,이자형성1：1형적췌합물.수 HNO3농도증가, Eu(Ⅲ)화 Am(Ⅲ)적췌취분배비증가.상동조건하, TOE-BisDGA 대 Eu(Ⅲ)화 Am(Ⅲ)적췌취능력강우 TOX-BisDGA.사솔분석표명 TOE-BisDGA 화 TOX-BisDGA 여 Eu(Ⅲ)화 Am(Ⅲ)균형성2：1형적췌합물.온도승고,췌취분배비하강,췌취반응시방열반응.2충 BisDGAs 대 Eu(Ⅲ)적친화력강우대 Am(Ⅲ)적친합력,표명 BisDGAs 대 Eu(Ⅲ)유일정적선택성.동시,연구료 BisDGAs 췌취 Eu(Ⅲ)화 Am(Ⅲ)적궤리,급출료표관췌취평형상수화췌취반응열역학함수△H,△S화△G 적치.차외,환대 TOE-BisDGA 화 TOX-BisDGA 여 Eu(Ⅲ)형성적배합물진행료홍외화자외광보분석.
Two bisdiglycolamides, N,N,N’’’,N’’’-tetraoctyl-N’,N″- ethanediyl bisdiglycolamide( TOE-Bis-DGA) and N,N,N’’’,N’’’-tetraoctyl-N’,N″-m-xylylene bisdiglycolamide( TOX-BisDGA), were synthesized by a mixed anhydrides method. Their extraction behaviors of Eu(Ⅲ) and Am(Ⅲ), as well as the extraction of nitric acid were investigated from nitric acid solution using kerosene / n-octanol( volume ratio 90 : 10) as diluent. Nitric acid was extracted as the form of HNO3 ·BisDGAs by BisDGAs at less than 1. 0 mol/ L HNO3 . The distribution ratios of Eu(Ⅲ) and Am(Ⅲ) increased with the increase of nitric acid concentration. TOE-BisDGA had a stronger extraction power for Eu(Ⅲ) and Am(Ⅲ) than TOX-BisDGA. Slope analyses showed that Eu( Ⅲ) and Am ( Ⅲ) were extracted as di-solvated species by BisDGAs. The distribution ratios of Eu(Ⅲ) and Am ( Ⅲ) decreased with temperature rise, which suggested that the extraction reaction of Eu(Ⅲ) and Am( Ⅲ) is exothermic. The two BisDGAs displayed a higher affinity toward Eu ( Ⅲ) than Am(Ⅲ). In the mean time, the extraction mechanism was described and the apparent extraction equilibrium constant as well as Gibbs free energy change, enthalpy change and entropy change were presented. In addi-tion, their Eu(Ⅲ) complexes were analyzed by IR and UV spectra.